Modified polymers and compositions containing the same

ABSTRACT

A first-order modified, hydrogenated polymer comprising (1) a hydrogenated polymer obtained by hydrogenating at least one unhydrogenated polymer selected from the group consisting of a polymer comprising conjugated diene monomer units and a copolymer comprising conjugated diene monomer units and vinyl aromatic hydrocarbon monomer units, and (2) a functional group-containing first-order modifier group bonded to the hydrogenated polymer (1), wherein the content of the vinyl aromatic hydrocarbon monomer units, vinyl aromatic hydrocarbon block ratio, weight average molecular weight, and hydrogenation ratio (as measured with respect to the double bonds in the conjugated diene monomer units) of the first-order modified, hydrogenated polymer are, respectively, within specific ranges. A second-order modified polymer obtained by reacting a second-order modifier with a first-order modified polymer comprising (β) a base polymer and (γ) a functional group-containing first-order modifier group bonded to the base polymer (β). A composition comprising the above-mentioned first-order modified, hydrogenated polymer or second-order modified polymer and at least one functional component other than the modified polymer.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a modified polymer and a compositioncontaining the same. More particularly, the present invention isconcerned with a first-order modified, hydrogenated polymer comprising(1) a hydrogenated polymer obtained by hydrogenating at least oneunhydrogenated polymer selected from the group consisting of a polymercomprising conjugated diene monomer units and a copolymer comprisingconjugated diene monomer units and vinyl aromatic hydrocarbon monomerunits, and (2) a functional group-containing first-order modifier groupbonded to the hydrogenated polymer (1), wherein the content of the vinylaromatic hydrocarbon monomer units, vinyl aromatic hydrocarbon blockratio, weight average molecular weight, and hydrogenation ratio (asmeasured with respect to the double bonds in the conjugated dienemonomer units) of the first-order modified, hydrogenated polymer are,respectively, within specific ranges. Further, the present invention isconcerned with a second-order modified polymer obtained by reacting asecond-order modifier with a first-order modified polymer comprising (β)a base polymer and (γ) a functional group-containing first-ordermodifier group bonded to the base polymer (β). Furthermore, the presentinvention is concerned with a composition comprising the above-mentionedfirst-order modified polymer or second-order modified polymer and atleast one component selected from various conventional additives (suchas inorganic fillers (e.g., silica), polymers other than theabove-mentioned modified polymers of the present invention, tackifiersand asphalts). The modified polymer of the present invention exhibitsstrong interaction with other various components, and by virtue of suchproperty, the modified polymer of the present invention can beadvantageously used for producing compositions, such as afiller-containing modified polymer composition, a modified polymercomposition comprising a thermoplastic resin and/or a rubbery polymer,an adhesive composition, an asphalt composition and a styrene resincomposition, which have excellent properties. Furthermore, the presentinvention is concerned with a precursor composition for use as aprecursor of a second-order modified polymer composition, wherein theprecursor composition comprises a first-order modified polymercomprising a base polymer (β) and a functional group-containingfirst-order modifier group (γ) bonded to the base polymer (γ), andfurther comprises a second-order modifier and at least one additionalcomponent selected from the group consisting of the above-mentionedadditives.

2. Prior Art

As a method for producing a polymer having a functional group,Unexamined Japanese Patent Application Laid-Open Specification No. Sho59-98106 (corresponding to U.S. Pat. No. 4,465,809) discloses a methodfor producing a carboxyl group-containing polymer, in which apolymer-alkali metal composition is contacted with an epoxy compound,and the resultant product is directly contacted with a cyclic acidanhydride, thereby obtaining a carboxyl group-containing polymer.However, such carboxyl group-containing polymer (which has a terminalepoxy compound residue having bonded thereto a cyclic acid anhydrideresidue) has poor affinity to a thermo-plastic resin and/or a rubberypolymer, an inorganic filler, a polar group-containing additive and thelike.

Unexamined Japanese Patent Application Laid-Open Specification No. Sho63-238107 (corresponding to U.S. Pat. No. 4,972,023) discloses a polymerwhich is modified with a terminal acid group (or a salt thereof) whichis bonded to the polymer through an acid amido group, and discloses amethod for producing the modified polymer as well as applications of themodified polymer. This modified polymer is obtained by a method in whichthe modification is performed using 1,5-diaza-bicylo[3.1.0]-hexane and aderivative thereof and a Schiff base derived from an aliphatic oraromatic amine and aldehyde. The modified polymer (which is modifiedwith a terminal acid group (or a salt thereof) which is bonded to thepolymer through an acid amido group) has poor affinity to athermoplastic resin and/or a rubbery polymer, an inorganic filler, apolar group-containing additive and the like.

Further, Unexamined Japanese Patent Application Laid-Open SpecificationNos. Hei 7-196728 and Hei 9-143224 discloses a modified hydrogenatedpolymer which is obtained by introducing a primary amino group or asecondary amino group into the terminals of a hydrogenated polymer.However, such modified polymer (which is modified with a terminal aminogroup) has poor affinity to a thermoplastic resin and/or a rubberypolymer, an inorganic filler, a polar group-containing additive and thelike.

In recent years, in the field of a tire tread rubber composition, atechnique of using silica as a substitute for carbon black has beenattracting much attention. However, this technique is accompanied byproblems. For example, silica has poor affinity to a rubber as comparedto that of conventional carbon black and, thus, the dispersibility ofsilica in a rubber is not always satisfactory. Such poor dispersibilityof silica is likely to cause problems, such as unsatisfactory abrasionresistance and strength characteristics for a tire tread. For improvingthe dispersibility of silica in a rubber, it is necessary to add asilane coupling agent (typically bis(triethoxypropyl)tetrasulfide) to acomposition of rubber and silica and mix the composition under specifictemperature conditions, wherein the number of the mixing operations isincreased.

In this situation, for improving the dispersibility of silica in arubber, a method for modifying a rubber with various terminalalkoxysilyl groups, and a silica-containing rubber compositioncomprising the modified rubber have been proposed in Unexamined JapanesePatent Application Laid-Open Specification No. Sho 62-227908, UnexaminedJapanese Patent Application Laid-Open Specification No. Hei 8-53513(corresponding to U.S. Pat. No. 5,665,812) and Unexamined JapanesePatent Application Laid-Open Specification No. Hei 8-53576(corresponding to U.S. Pat. No. 6,204,322).

Further, a silica-containing composition comprising an epoxidizedpolymer is proposed in Unexamined Japanese Patent Application Laid-OpenSpecification No. Hei 9-118785 (corresponding to EP763564). In addition,Unexamined Japanese Patent Application Laid-Open Specification No. Hei7-330959 discloses a tire tread composition comprising an SBR(styrene-butadiene rubber) having a specific molecular structure,wherein the SBR has been modified by coupling a multifunctional compoundhaving a diglicidylamino group. This tire tread composition was proposedin an attempt to provide a tire tread composition having increasedprocessability, reduced rolling resistance and improved wet skidresistance.

The rubber material used in the above-mentioned rubber compositions hasmany unsaturated double bonds in the polymer chain thereof and,therefore, exhibits poor heat resistance and weatherability. As aconjugated diene polymer having excellent heat resistance andweatherability, Unexamined Japanese Patent Application Laid-OpenSpecification No. Sho 63-41547 discloses a hydrogenated polymer which ismodified with a specific functional group. This patent document alsodiscloses a method for improving the properties of a carbon-containingcomposition, in which a functional group (such as an amino group) whichinteracts with carbon is addition-bonded to a hydrogenated polymer.Further, WO96/05250 (corresponding to U.S. Pat. No. 5,804,644) disclosesa silica-containing rubber composition comprising a hydrogenated rubber.However, the technique disclosed in this patent document is aimed at arubber composition containing a rubber having low hydrogenation ratiowhich is suitable for producing tires. Therefore, the improvements inthe heat resistance and weatherability of the rubber composition areunsatisfactory for use in fields other than tire production.

Unexamined Japanese Patent Application Laid-Open Specification No. Hei2-60948 discloses a rubber composition having excellent heat resistanceand weather-ability. Further, each of Unexamined Japanese PatentApplication Laid-Open Specification Nos. Sho 62-283105 and Sho 63-41547and Unexamined Japanese Patent Application Laid-Open Specification No.Hei 3-74409 (corresponding to U.S. Pat. No. 5,216,074) discloses ahydrogenated modified polymer. The dispersibiltiy and reinforcing effectof silica which are imparted by the techniques disclosed in theabove-mentioned patent documents are unsatisfactory and, moreover, thecomposition and polymer exhibit only poor properties with respect toprocessability, low heat build-up and abrasion resistance.

In the fields of sheets, films and other shaped articles which areproduced from polymeric materials, there have been made a number ofproposals in which there is used a polymer composition or laminatecomprising a plurality of types of polymeric materials in order toobtain advantages in that a satisfactory strength is imparted to thesheets, films or the like, or the processability of the sheets, films orthe like is improved, or the production cost of the sheets, films or thelike is reduced. However, when producing a polymer composition by mixingdifferent polymeric materials together, the number of combinations ofdifferent polymeric materials which exhibit good compatibility with eachother, is limited. In the case of a polymer composition comprisingdifferent polymeric materials which exhibit poor compatibility with eachother, a problem is likely to arise in that, due to the poorcompatibility, the composition becomes non-homogeneous, and adelamination occurs between layers of different polymeric materials,thus rendering it impossible to obtain a satisfactory improving effectaimed at by using a combination of different polymeric materials.

It is well known that, as a component for improving the miscibility ofpolymeric materials, there is used a polymeric material having afunctional group. For example, Unexamined Japanese Patent ApplicationLaid-Open Specification No. Hei 2-60948 discloses a compositioncomprising a modified hydrogenated diene polymer having a functionalgroup and a flexible elastomer, wherein the modified hydrogenated dienepolymer is obtained by an addition reaction between a functionalgroup-containing unsaturated compound and a hydrogenated diene polymerin the presence of a radical initiator. Further, Unexamined JapanesePatent Application Laid-Open Specification No. Hei 3-74409(corresponding to U.S. Pat. No. 5,216,074) discloses a thermoplasticpolymer composition comprising a modified hydrogenated block polymerhaving a functional group and a thermoplastic resin and/or a rubberypolymer, wherein the modified hydrogenated block polymer is obtained byan addition reaction between a functional group-containing unsaturatedcompound and a hydrogenated block polymer in the presence of a radicalinitiator.

An asphalt composition is used in wide variety of fields, such as amaterial for road paving, a water-proof sheet, a noise insulation sheetand a roofing sheet. In these fields, many attempts have been made toimprove the properties of an asphalt by adding various polymers to theasphalt.

However, in recent years, due to the expansion of traffic and theincrease in the number of expressways, there is a demand for an asphaltcomposition which can form a road pavement layer having excellentstrength and abrasion resistance. Further, there is a growing demand foran asphalt composition which can form a road pavement layer having notonly excellent strength and abrasion resistance, but also high opengraded (void fraction) for improving drainage and noise reductionproperties of expressways.

Recently, from the viewpoint of preventing environmental pollution andmaintaining labor environment, the use of a hot-melt adhesive isexpanding. However, the balance between retention and adhesion of theconventional hot-melt adhesive is unsatisfactory. For improving theproperties of a hot-melt adhesive, each of Unexamined Japanese PatentApplication Laid-Open Specification Nos. Sho 64-81877 and 61-278578 and“Sechaku (Adhesion)” Vol.32, No.1, page 27 (published in 1988) disclosesan adhesive composition comprising a triblock copolymer and a diblockcopolymer. However, the improvements achieved by the techniquesdisclosed in these patent documents were unsatisfactory.

A polystyrene having not only excellent stiffness, transparency andluster, but also good processability, is used in various fields.However, a polystyrene has a major defect, namely poor impactresistance. For alleviating this defect, various non-vulcanized rubbersare used as an impact-modifier for a styrene resin composition. Amongthe known styrene resin compositions containing a non-vulcanized rubber,a styrene resin composition obtained by subjecting a styrene monomer toradical polymerization in the presence of a nonvulcanized rubber, whichcomposition comprises a rubbery polymer having a styrene monomergraft-polymerized thereto, has been manufactured widely in commercialscale.

In connection with the above-mentioned method, a method for improvingthe impact resistance and appearance of a styrene resin composition bythe use of a modified conjugated diene polymer has been disclosed inUnexamined Japanese Patent Application Laid-Open Specification Nos. Sho57-94014, Sho 63-8411, Sho 63-278920 and Hei 6-228246. From the detailedstudies of the methods disclosed in these patent documents, it becameapparent that none of the produced styrene resin composition exhibitexcellent balance between the impact resistance and appearance which issatisfactory for practical use.

SUMMARY OF THE INVENTION

In this situation, the present inventors have made extensive andintensive studies with a view toward solving the above-mentionedproblems accompanying the prior art. As a result, it has unexpectedlybeen found that the above-mentioned problems can be solved by afirst-order modified, hydrogenated polymer comprising: (1) ahydrogenated polymer obtained by hydrogenating at least oneunhydrogenated polymer selected from the group consisting of (1-A) apolymer comprising conjugated diene monomer units and (1-B) a copolymercomprising conjugated diene monomer units and vinyl aromatic hydrocarbonmonomer units, the copolymer (1-B) having no or at least one polymerblock (H) of the vinyl aromatic hydrocarbon monomer units, and (2) afunctional group-containing first-order modifier group bonded to thehydrogenated polymer (1), wherein the functional group-containingfirst-order modifier group comprises at least one functional groupselected from the group consisting of a hydroxyl group, an epoxy group,an amino group, a silanol group and an alkoxysilane group, and whereinthe content of the vinyl aromatic hydrocarbon monomer units, vinylaromatic hydrocarbon block ratio, weight average molecular weight andhydrogenation ratio (as measured with respect to the double bonds in theconjugated diene monomer units) of the first-order modified,hydrogenated polymer are, respectively, within specific ranges. Further,the present inventors found that the above-mentioned problems can bealso solved by a second-order modified polymer obtained by reacting asecond-order modifier with a first-order modified polymer comprising (β)a base polymer and (γ) a functional group-containing first-ordermodifier group bonded to the base polymer (β). The present invention hasbeen completed based on these novel findings.

Accordingly, it is an object of the present invention to provide afirst-order modified, hydrogenated polymer and a second-order modifiedpolymer which can be advantageously used for producing compositions,such as a filler-containing modified polymer composition, a modifiedpolymer composition comprising a thermoplastic resin and/or a rubberypolymer, an adhesive composition, an asphalt composition and a styreneresin composition, which have excellent properties.

It is another object of the present invention to provide afiller-containing modified polymer composition, a modified polymercomposition, an adhesive composition, an asphalt composition and astyrene resin composition, each comprising the above-mentionedfirst-order modified, hydrogenated polymer or the above-mentionedsecond-order modified polymer.

It is still another object of the present invention to provide aprecursor composition for use as a precursor of a second-order modifiedpolymer composition comprising the above-mentioned second-order modifiedpolymer, wherein the precursor composition comprises a first-ordermodified polymer comprising a base polymer (β) and a functionalgroup-containing first-order modifier group (γ) bonded to the basepolymer (β), and further comprises a second-order modifier and at leastone component other than the above-mentioned modified polymer or amodifier.

The foregoing and other objects, features and advantages of the presentinvention will be apparent from the following detailed description andappended claims.

DETAILED DESCRIPTION OF THE INVENTION

In one aspect of the present invention, there is provided a first-ordermodified, hydrogenated polymer comprising:

-   -   (1) a hydrogenated polymer obtained by hydrogenating at least        one unhydrogenated polymer selected from the group consisting of        (1-A) a polymer comprising conjugated diene monomer units and        (1-B) a copolymer comprising conjugated diene monomer units and        vinyl aromatic hydrocarbon monomer units, the copolymer (1-B)        having no or at least one polymer block (H) of the vinyl        aromatic hydrocarbon monomer units, and    -   (2) a functional group-containing first-order modifier group        bonded to the hydrogenated polymer (1), wherein the functional        group-containing first-order modifier group comprises at least        one functional group selected from the group consisting of a        hydroxyl group, an epoxy group, an amino group, a silanol group        and an alkoxysilane group,    -   the first-order modified, hydrogenated polymer having the        following characteristics (i) to (iv):    -   (i) a content of the vinyl aromatic hydrocarbon monomer units of        from 0 to 60% by weight, based on the weight of the hydrogenated        polymer,    -   (ii) a vinyl aromatic hydrocarbon block ratio of from 0 to less        than 50% by weight, wherein the vinyl aromatic hydrocarbon block        ratio is defined as the percent by weight of the vinyl aromatic        hydrocarbon monomer units contained in the at least one polymer        block (H) of the vinyl aromatic hydrocarbon monomer units, based        on the total weight of vinyl aromatic hydrocarbon monomer units        contained in the copolymer (1-B),    -   (iii) a weight average molecular weight of from 20,000 to        2,000,000, and    -   (iv) a hydrogenation ratio of more than 70%, as measured with        respect to the double bonds in the conjugated diene monomer        units.

For easy understanding of the present invention, the essential featuresand various preferred embodiments of the present invention areenumerated below.

1. A first-order modified, hydrogenated polymer comprising:

-   -   (1) a hydrogenated polymer obtained by hydrogenating at least        one unhydrogenated polymer selected from the group consisting of        (1-A) a polymer comprising conjugated diene monomer units and        (1-B) a copolymer comprising conjugated diene monomer units and        vinyl aromatic hydrocarbon monomer units, the copolymer (1-B)        having no or at least one polymer block (H) of the vinyl        aromatic hydrocarbon monomer units, and    -   (2) a functional group-containing first-order modifier group        bonded to the hydrogenated polymer (1), wherein the functional        group-containing first-order modifier group comprises at least        one functional group selected from the group consisting of a        hydroxyl group, an epoxy group, an amino group, a silanol group        and an alkoxysilane group,    -   the first-order modified, hydrogenated polymer having the        following characteristics (i) to (iv):    -   (i) a content of the vinyl aromatic hydrocarbon monomer units of        from 0 to 60% by weight, based on the weight of the hydrogenated        polymer,    -   (ii) a vinyl aromatic hydrocarbon block ratio of from 0 to less        than 50% by weight, wherein the vinyl aromatic hydrocarbon block        ratio is defined as the percent by weight of the vinyl aromatic        hydrocarbon monomer units contained in the at least one polymer        block (H) of the vinyl aromatic hydrocarbon monomer units, based        on the total weight of vinyl aromatic hydrocarbon monomer units        contained in the copolymer (1-B),    -   (iii) a weight average molecular weight of from 20,000 to        2,000,000, and    -   (iv) a hydrogenation ratio of more than 70%, as measured with        respect to the double bonds in the conjugated diene monomer        units.

2. The first-order modified, hydrogenated polymer according to item 1above, wherein the functional group-containing first-order modifiergroup (2) comprises at least one functional group represented by aformula selected from the group consisting of the following formulae (a)to (m):

-   -   wherein, in the formulae (a) to (m):        -   N represents a nitrogen atom, Si represents a silicon atom,            O represents an oxygen atom, C represents a carbon atom, and            H represents a hydrogen atom,        -   each of R¹ to R⁴ independently represents a hydrogen atom or            a C₁-C₂₄ hydrocarbon group which optionally has at least one            functional group selected from the group consisting of a            hydroxyl group, an epoxy group, an amino group, a silanol            group and a C₁-C₂₄ alkoxysilane group,        -   each R⁵ independently represents a C₁-C₄₈ hydrocarbon group            and optionally, independently has at least one functional            group selected from the group consisting of a hydroxyl            group, an epoxy group, an amino group, a silanol group and a            C₁-C₂₄ alkoxysilane group,        -   each R⁶ independently represents a hydrogen atom or a C₁-C₈            alkyl group,        -   wherein each of R¹ to R⁵ optionally, independently has            bonded thereto at least one atom selected from the group            consisting of an oxygen atom, a nitrogen atom, a sulfur atom            and a silicon atom, the at least one atom being present in a            linkage other than a hydroxyl group, an epoxy group, an            amino group, a silanol group and an alkoxysilane group.

3. The first-order modified, hydrogenated polymer according to item 1 or2 above, which is represented by a formula selected from the groupconsisting of the following formulae (I) to (V):

-   -   wherein:    -   A¹ represents a unit which is represented by any one of the        following formulae (a-1) and (b-1):    -   B¹ represents a unit which is represented by the following        formula (c-1):    -   C¹ represents a unit which is represented by any one of the        following formulae (d-1) and (e-1):    -   D¹ represents a unit which is represented by the following        formula (f-1):        —R⁸—NHR³   (f-1),    -   E¹ represents a unit which is represented by the following        formula (g-1):        —R⁹—P¹, and   (g-1)    -   F¹ represents a unit which is represented by any one of the        following formulae (h-1) to (j-1):    -   wherein, in the formulae (I) to (III) and (a-1) to (j-1):        -   N represents a nitrogen atom, Si represents a silicon atom,            O represents an oxygen atom, C represents a carbon atom, and            H represents a hydrogen atom,        -   P¹ represents the hydrogenated polymer (1),        -   R^(1a) represents a trivalent aliphatic C₁-C₄₈ hydrocarbon            group,        -   each of R^(1b), R⁴, R⁸ to R¹⁰ and R¹³ to R¹⁵ independently            represents a C₁-C₄₈ alkylene group,        -   each of R², R³ and R¹¹ independently represents a C₁-C₄₈            alkyl group, a C₆-C₄₈ aryl group, an alkylaryl group            comprised of C₁-C₄₈ alkyl and C₆-C₄₈ aryl, an aralkyl group            comprised of C₁-C₄₈ alkyl and C₆-C₄₈ aryl, or a C₃-C₄₈            cycloalkyl group,        -   wherein each of R^(1a), R^(1b), R³, R⁴, R⁸ to R¹⁰ and R¹³ to            R¹⁵ optionally, independently has at least one functional            group selected from the group consisting of a hydroxyl            group, an epoxy group, an amino group, a silanol group and a            C₁-C₂₄ alkoxysilane group,        -   each of R⁵ to R⁷ and R¹² independently represents a hydrogen            atom, a C₁-C₄₈ alkyl group, a C₆-C₄₈ aryl group, an            alkylaryl group comprised of C₁-C₄₈ alkyl and C₆-C₄₈ aryl,            an aralkyl group comprised of C₁-C₄₈ alkyl and C₆-C₄₈ aryl,            or a C₃-C₄₈ cyclo-alkyl group,        -   wherein each of R^(1a), R^(1b), R² to R⁴ and R⁸ to R¹⁵            optionally, independently has bonded thereto at least one            atom selected from the group consisting of an oxygen atom, a            nitrogen atom, a sulfur atom and a silicon atom, the at            least one atom being present in a linkage other than a            hydroxyl group, an epoxy group, an amino group, a silanol            group and an alkoxy-silane group, and        -   each of k, l, m and o is independently an integer of 0 or            more, provided that both k and l are not simultaneously 0,            and n is an integer of 1 or more.

4. A filler-containing modified polymer composition comprising:

-   -   100 parts by weight of (A-1) the first-order modified,        hydrogenated polymer of any one of items 1 to 3 above, and    -   0.5 to 300 parts by weight of (B) a reinforcing filler.

5. The filler-containing modified polymer composition according to item4 above, which further comprises 0.01 to 20 parts by weight of (C) asecond-order modifier having a functional group which is reactive to thefunctional group of the modifier group of the first-order modified,hydrogenated polymer (A-1), wherein the second-order modifier (C) is atleast one member selected from the group consisting of a functionalmonomer and a functional oligomer.

6. The filler-containing modified polymer composition according to item4 or 5 above, wherein the reinforcing filler (B) is at least one memberselected from the group consisting of a silica inorganic filler, a metaloxide, a metal hydroxide and carbon.

7. A crosslinked, filler-containing modified polymer compositionobtained by subjecting the filler-containing modified polymercomposition of any one of items 4 to 6 above to a crosslinking reactionin the presence of a vulcanizing agent.

8. A modified polymer composition comprising:

-   -   1 to 99 parts by weight, relative to 100 parts by weight of the        total of components (A-1) and (D), of (A-1) the first-order        modified, hydrogenated polymer of any one of items 1 to 3 above,        and    -   99 to 1 part by weight, relative to 100 parts by weight of the        total of components (A-1) and (D), of (D) at least one polymer        selected from the group consisting of a thermoplastic resin        other than the first-order modified, hydrogenated polymer (A-1)        and a rubbery polymer other than the first-order modified,        hydrogenated polymer (A-1).

9. The modified polymer composition according to item 8 above, whichfurther comprises 0.01 to 20 parts by weight, relative to 100 parts byweight of the total of components (A-1) and (D), of (C) a second-ordermodifier having a functional group which is reactive to the functionalgroup of the modifier group of the first-order modified, hydrogenatedpolymer (A-1), wherein the second-order modifier (C) is at least onemember selected from the group consisting of a functional monomer and afunctional oligomer.

10. The modified polymer composition according to item 8 or 9 above,wherein the rubbery polymer in component (D) comprises at least onemember selected from the group consisting of a conjugated diene polymercomprising conjugated diene monomer units, a random copolymer comprisingconjugated diene monomer units and vinyl aromatic hydrocarbon monomerunits, a block copolymer comprising conjugated diene monomer units andvinyl aromatic hydrocarbon monomer units, a non-diene polymer and anatural rubber,

-   -   the rubbery polymer being unhydrogenated or at least partially        hydrogenated.

11. The modified polymer composition according to any one of items 8 to10 above, wherein the thermoplastic resin in component (D) is afunctional group-containing thermoplastic resin and the rubbery polymerin component (D) is a functional group-containing rubbery polymer,wherein each of the functional group-containing thermoplastic resin andrubbery polymer contains at least one functional group which is reactiveto the functional group of the first-order modifier group of thefirst-order modified, hydrogenated polymer (A-1).

12. The modified polymer composition according to item 11 above, whereinthe functional group-containing thermoplastic resin comprises at leastone member selected from the group consisting of a polyester resin, apolyamide resin, a polycarbonate resin, a polyurethane resin, apolyphenylene ether resin and a polyoxymethylene resin each of whichcontains at least one functional group selected from the groupconsisting of an acid anhydride group, a carboxyl group, a hydroxylgroup, an epoxy group, an amino group, a silanol group and analkoxysilane group.

13. An adhesive composition comprising:

-   -   100 parts by weight of (A-1) the first-order modified,        hydrogenated polymer of any one of items 1 to 3 above, and    -   20 to 400 parts by weight of (E) a tackifier.

14. The adhesive composition according to item 13 above, which furthercomprises 0.01 to 20 parts by weight of (C) a second-order modifierhaving a functional group which is reactive to the functional group ofthe modifier group of the first-order modified, hydrogenated polymer(A-1), wherein the second-order modifier (C) is at least one memberselected from the group consisting of a functional monomer and afunctional oligomer.

15. An asphalt composition comprising:

-   -   0.5 to 50 parts by weight of (A-1) the first-order modified,        hydrogenated polymer of any one of items 1 to 3 above, and    -   100 parts by weight of (F) an asphalt.

16. The asphalt composition according to item 15 above, which furthercomprises 0.01 to 20 parts by weight of (C) a second-order modifierhaving a functional group which is reactive to the functional group ofthe modifier group of the first-order modified, hydrogenated polymer(A-1), wherein the second-order modifier (C) is at least one memberselected from the group consisting of a functional monomer and afunctional oligomer.

17. A styrene resin composition obtained by subjecting a raw materialmixture to radical polymerization, the raw material mixture comprising:

-   -   2 to 30 parts by weight, relative to 100 parts by weight of the        total of components (A-1) and (G), of (A-1) the first-order        modified, hydrogenated polymer of any one of items 1 to 3 above,        and    -   98 to 70 parts by weight, relative to 100 parts by weight of the        total of components (A-1) and (G), of (G) a vinyl aromatic        hydrocarbon monomer or a mixture of a vinyl aromatic hydrocarbon        monomer and a comonomer copolymerizable with the vinyl aromatic        hydrocarbon monomer.

18. The styrene resin composition according to item 17 above, whereinthe raw material mixture further comprises 0.01 to 20 parts by weight,relative to 100 parts by weight of the total of components (A-1) and(G), of (C) a second-order modifier having a functional group which isreactive to the functional group of the modifier group of thefirst-order modified, hydrogenated polymer (A-1), wherein thesecond-order modifier (C) is at least one member selected from the groupconsisting of a functional monomer and a functional oligomer.

19. A method for producing the styrene resin composition of item 17 or18 above, comprising:

-   -   (1) providing a raw material mixture comprising (A-1) the        first-order modified, hydrogenated polymer of any one of items 1        to 3 above, (G) a vinyl aromatic hydrocarbon monomer or a        mixture of a vinyl aromatic hydrocarbon monomer and a comonomer        copolymerizable with the vinyl aromatic hydrocarbon monomer, and        optionally at least one member selected from the group        consisting of (C) a second-order modifier and (B) a reinforcing        filler, and    -   (2) subjecting the raw material mixture to radical        polymerization,    -   thereby obtaining a styrene resin composition.

20. A second-order modified polymer comprising:

-   -   (β) a base polymer, and    -   (δ) a functional group-containing modifier group bonded to the        base polymer (β),    -   wherein the second-order modified polymer is obtained by        reacting a second-order modifier with a first-order modified        polymer comprising (β) a base polymer and (γ) a functional        group-containing first-order modifier group bonded to the base        polymer (β) to thereby form (δ) a functional group-containing        modifier group, wherein the second-order modifier has a        functional group which is reactive to the functional group of        the first-order modifier group (γ) of the first-order modified        polymer, and wherein the second-order modifier is used in an        amount of 0.3 to 10 moles, relative to one equivalent of the        functional group of the first-order modifier group (γ) of the        first-order modified polymer,    -   the second-order modifier being at least one member selected        from the group consisting of a functional monomer and a        functional oligomer,        -   wherein the base polymer (β) of the first-order modified            polymer is unhydrogenated or at least partially hydrogenated            and is at least one member selected from the group            consisting of the following polymers (β-1) to (β-3):            -   (β-1) a conjugated diene polymer comprising conjugated                diene monomer units,            -   (β-2) a copolymer comprising conjugated diene monomer                units and vinyl aromatic hydrocarbon monomer units, the                copolymer having no or at least one polymer block (H) of                the vinyl aromatic hydrocarbon monomer units, wherein                the copolymer has a vinyl aromatic hydrocarbon block                ratio of from 0 to less than 50% by weight, the vinyl                aromatic hydrocarbon block ratio being defined as the                percent by weight of the vinyl aromatic hydrocarbon                monomer units contained in the at least one polymer                block (H) of the vinyl aromatic hydrocarbon monomer                units, based on the total weight of vinyl aromatic                hydrocarbon monomer units contained in the copolymer as                in the unhydrogenated state, and            -   (β-3) a vinyl aromatic hydrocarbon polymer comprising                vinyl aromatic hydrocarbon monomer units, and        -   wherein the functional group-containing first-order modifier            group (γ) of the first-order modified polymer comprises at            least one functional group represented by a formula selected            from the group consisting of the above-mentioned            formulae (a) to (m).

21. The second-order modified polymer according to item 20 above,wherein the first-order modified polymer is represented by a formulaselected from the group consisting of the above-mentioned formulae (I)to (V).

22. The second-order modified polymer according to item 20 or 21 above,wherein each of the functional monomer and the functional oligomer hasat least one functional group selected from the group consisting of ahydroxyl group, an amino group, a carboxyl group, an acid anhydridegroup, an isocyanate group, an epoxy group, a silanol group and analkoxysilane group.

23. The second-order modified polymer according to any one of items 20to 22 above, which is represented by a formula selected from the groupconsisting of the following formulae (VI) to (X):

-   -   wherein:    -   A² represents a unit which is represented by any one of the        following formulae (a-2) and (b-2):    -   B² represents a unit which is represented by any one of the        following formulae (c-2) to (e-2):    -   C² represents a unit which is represented by any one of the        following formulae (f-2) to (h-2):    -   D² represents a unit which is represented by the following        formula (i-2):        —R⁸—NR³—X¹,   (i-2)    -   E² represents a unit which is represented by the following        formula (j-2):        —R⁹—P¹, and   (j-2)    -   F² represents a unit which is represented by any one of the        following formulae (k-2) to (m-2): d    -   wherein:    -   X¹ represents a unit which is represented by any one of the        following formulae (n-2) to (s-2):    -   wherein, in the formulae (VI) to (VIII) and (a-2) to (s-2):        -   N represents a nitrogen atom, Si represents a silicon atom,            O represents an oxygen atom, C represents a carbon atom, and            H represents a hydrogen atom,        -   P¹ represents the base polymer,        -   R^(1a) represents a trivalent aliphatic C₁-C₄₈ hydrocarbon            group,        -   each of R^(1b), R⁴, R⁸ to R¹⁰ and R¹³ to R²⁰ independently            represents a C₁-C₄₈ alkylene group,        -   each of R², R³ and R¹¹ independently represents a C₁-C₄₈            alkyl group, a C₆-C₄₈ aryl group, an alkylaryl group            comprised of C₁-C₄₈ alkyl and C₆-C₄₈ aryl, an aralkyl group            comprised of C₁-C₄₈ alkyl and C₆-C₄₈ aryl, or a C₃-C₄₈            cycloalkyl group,        -   wherein each of R^(1a), R^(1b), R³, R⁴, R⁸ to R¹⁰, R¹³ to            R¹⁵ and R¹⁷ to R²⁰ optionally, independently has at least            one functional group selected from the group consisting of a            hydroxyl group, an epoxy group, an amino group, a silanol            group and a C₁-C₂₄ alkoxysilane group,        -   each of R⁵ to R⁷ and R¹² independently represents a hydrogen            atom, a C₁-C₄₈ alkyl group, a C₆-C₄₈ aryl group, an            alkylaryl group comprised of C₁-C₄₈ alkyl and C₆-C₄₈ aryl,            an aralkyl group comprised of C₁-C₄₈ alkyl and C₆-C₄₈ aryl,            or a C₃-C₄₈ cycloalkyl group,        -   wherein each of R^(1a), R^(1b), R² to R⁴ and R⁸ to R20            optionally, independently has bonded thereto at least one            atom selected from the group consisting of an oxygen atom, a            nitrogen atom, a sulfur atom, and a silicon atom, the at            least one atom being present in a linkage other than a            hydroxyl group, an epoxy group, an amino group, a silanol            group and an alkoxysilane group, and        -   each of t, u, v and x is independently an integer of 0 or            more, provided that both t and u are not simultaneously 0,            and each of w, y, z and α is independently an integer of 1            or more.

24. A method for producing the second-order modified polymer of any oneof items 20 to 23 above, comprising:

-   -   (1) providing a first-order modified polymer comprising:        -   (β) a base polymer which is unhydrogenated or at least            partially hydrogenated and which is at least one member            selected from the group consisting of the following polymers            (β-1) to (β-3):            -   (β-1) a conjugated diene polymer comprising conjugated                diene monomer units,            -   (β-2) a copolymer comprising conjugated diene monomer                units and vinyl aromatic hydrocarbon monomer units, the                copolymer having no or at least one polymer block (H) of                the vinyl aromatic hydrocarbon monomer units, wherein                the copolymer has a vinyl aromatic hydrocarbon block                ratio of from 0 to less than 50% by weight, the vinyl                aromatic hydrocarbon block ratio being defined as the                percent by weight of the vinyl aromatic hydrocarbon                monomer units contained in the at least one polymer                block (H) of the vinyl aromatic hydrocarbon monomer                units, based on the total weight of vinyl aromatic                hydrocarbon monomer units contained in the copolymer as                in the unhydrogenated state, and            -   (β-3) a vinyl aromatic hydrocarbon polymer comprising                vinyl aromatic hydrocarbon monomer units, and        -   (γ) a functional group-containing first-order modifier group            bonded to the base polymer (β),        -   wherein the first-order modified polymer is produced by a            process in which a base polymer having a living terminal is            produced by a living anionic polymerization using an            organolithium compound as a polymerization catalyst, and a            functional group-containing first-order modifier is            addition-bonded to the living terminal of the base polymer            to obtain a first-order modified polymer, optionally            followed by partial or complete hydrogenation of the            obtained first-order modified polymer, and    -   (2) reacting a second-order modifier with the first-order        modified polymer to thereby form (δ) a functional        group-containing modifier group, wherein the second-order        modifier has a functional group which is reactive to the        functional group of the first-order modifier group (γ) of the        first-order modified polymer, and wherein the second-order        modifier is used in an amount of 0.3 to 10 moles, relative to        one equivalent of the functional group of the first-order        modifier group (γ) of the first-order modified polymer,    -   thereby obtaining a second-order modified polymer,        -   wherein the functional group-containing first-order modifier            group (γ) of the first-order modified polymer comprises at            least one functional group represented by a formula selected            from the group consisting of the above-mentioned            formulae (a) to (m).

25. A filler-containing modified polymer composition comprising:

-   -   100 parts by weight of (A-2) the second-order modified polymer        of any one of items 20 to 23 above, and    -   0.5 to 300 parts by weight of (B) a reinforcing filler.

26. The filler-containing modified polymer composition according to item25 above, wherein the reinforcing filler (B) is at least one memberselected from the group consisting of a silica inorganic filler, a metaloxide, a metal hydroxide and carbon.

27. A crosslinked, filler-containing modified polymer compositionobtained by subjecting the filler-containing modified polymercomposition of item 25 or 26 above to a crosslinking reaction in thepresence of a vulcanizing agent.

28. A modified polymer composition comprising:

-   -   1 to 99 parts by weight, relative to 100 parts by weight of the        total of components (A-2) and (D), of (A-2) the second-order        modified polymer of any one of items 20 to 23 above, and    -   99 to 1 part by weight, relative to 100 parts by weight of the        total of components (A-2) and (D), of (D) at least one polymer        selected from the group consisting of a thermoplastic resin        other than the second-order modified polymer (A-2) and a rubbery        polymer other than the second-order modified polymer (A-2).

29. The modified polymer composition according to item 28 above, whereinthe thermoplastic resin in component (D) comprises at least one memberselected from the group consisting of a polyester resin, a polyamideresin, a polycarbonate resin, a polyurethane resin, a polyphenyleneether resin and a polyoxymethylene resin each of which contains at leastone functional group selected from the group consisting of an acidanhydride group, a carboxyl group, a hydroxyl group, an epoxy group, anamino group, a silanol group and an alkoxysilane group.

30. A crosslinked, modified polymer composition obtained by subjectingthe modified polymer composition of any one of item 28 or 29 above tomelt-kneading in the presence of a vulcanizing agent.

31. An adhesive composition comprising:

-   -   100 parts by weight of (A-2) the second-order modified polymer        of any one of items 20 to 23 above, and    -   20 to 400 parts by weight of (E) a tackifier.

32. An asphalt composition comprising:

-   -   0.5 to 50 parts by weight of (A-2) the second-order modified        polymer of any one of items 20 to 23 above, and    -   100 parts by weight of (F) an asphalt.

33. A styrene resin composition obtained by subjecting a raw materialmixture to radical polymerization, the raw material mixture comprising:

-   -   2 to 30 parts by weight, relative to 100 parts by weight of the        total of components (A-2) and (G), of (A-2) the second-order        modified polymer of any one of items 20 to 23 above, and    -   98 to 70 parts by weight, relative to 100 parts by weight of the        total of components (A-2) and (G), of (G) a vinyl aromatic        hydrocarbon monomer or a mixture of a vinyl aromatic hydrocarbon        monomer and a comonomer copolymerizable with the vinyl aromatic        hydrocarbon monomer.

34. The styrene resin composition according to item 33 above, whereinthe raw material mixture further comprises 0.5 to 300 parts by weight,relative to 100 parts by weight of component (A-2), of (B) a reinforcingfiller.

35. The styrene resin composition according to item 34 above, whereinthe reinforcing filler (B) is at least one member selected from thegroup consisting of a silica inorganic filler, a metal oxide, a metalhydroxide and carbon.

36. A filler-containing modified polymer composition comprising:

-   -   100 parts by weight of (A-3) a first-order modified polymer        comprising:        -   (β) a base polymer which is unhydrogenated or at least            partially hydrogenated and which is at least one member            selected from the group consisting of the following polymers            (β-1) to (β-3):            -   (β-1) a conjugated diene polymer comprising conjugated                diene monomer units,            -   (β-2) a copolymer comprising conjugated diene monomer                units and vinyl aromatic hydrocarbon monomer units, the                copolymer having no or at least one polymer block (H) of                the vinyl aromatic hydrocarbon monomer units, wherein                the copolymer has a vinyl aromatic hydrocarbon block                ratio of from 0 to less than 50% by weight, the vinyl                aromatic hydrocarbon block ratio being defined as the                percent by weight of the vinyl aromatic hydrocarbon                monomer units contained in the at least one polymer                block (H) of the vinyl aromatic hydrocarbon monomer                units, based on the total weight of vinyl aromatic                hydrocarbon monomer units contained in the copolymer as                in the unhydrogenated state, and            -   (β-3) a vinyl aromatic hydrocarbon polymer comprising                vinyl aromatic hydrocarbon monomer units, and        -   (γ) a functional group-containing first-order modifier group            bonded to the base polymer (β),    -   0.5 to 300 parts by weight of (B) a reinforcing filler, and    -   0.01 to 20 parts by weight of (C) a second-order modifier having        a functional group which is reactive to the functional group of        the first-order modifier group (γ) of the first-order modified        polymer (A-3), wherein the second-order modifier (C) is at least        one member selected from the group consisting of a functional        monomer and a functional oligomer,        -   wherein the functional group-containing first-order modifier            group (γ) of the first-order modified polymer (A-3)            comprises at least one functional group represented by a            formula selected from the group consisting of the            above-mentioned formulae (a) to (m).

37. The filler-containing modified polymer composition according to item36 above, wherein the reinforcing filler (B) is at least one memberselected from the group consisting of a silica inorganic filler, a metaloxide, a metal hydroxide and carbon.

38. A crosslinked, filler-containing modified polymer compositionobtained by subjecting the filler-containing modified polymercomposition of item 36 or 37 above to a crosslinking reaction in thepresence of a vulcanizing agent.

39. A modified polymer composition comprising:

-   -   1 to 99 parts by weight, relative to 100 parts by weight of the        total of components (A-3) and (D), of (A-3) a first-order        modified polymer comprising:        -   (β) a base polymer which is unhydrogenated or at least            partially hydrogenated and which is at least one member            selected from the group consisting of the following polymers            (β-1) to (β-3):            -   (β-1) a conjugated diene polymer comprising conjugated                diene monomer units,            -   (β-2) a copolymer comprising conjugated diene monomer                units and vinyl aromatic hydrocarbon monomer units, the                copolymer having no or at least one polymer block (H) of                the vinyl aromatic hydrocarbon monomer units, wherein                the copolymer has a vinyl aromatic hydrocarbon block                ratio of from 0 to less than 50% by weight, the vinyl                aromatic hydrocarbon block ratio being defined as the                percent by weight of the vinyl aromatic hydrocarbon                monomer units contained in the at least one polymer                block (H) of the vinyl aromatic hydrocarbon monomer                units, based on the total weight of vinyl aromatic                hydrocarbon monomer units contained in the copolymer as                in the unhydrogenated state, and            -   (β-3) a vinyl aromatic hydrocarbon polymer comprising                vinyl aromatic hydrocarbon monomer units, and        -   (γ) a functional group-containing first-order modifier group            bonded to the base polymer (β),    -   99 to 1 part by weight, relative to 100 parts by weight of the        total of components (A-3) and (D), of (D) at least one polymer        selected from the group consisting of a thermoplastic resin        other than the first-order modified polymer (A-3) and a rubbery        polymer other than the first-order modified polymer (A-3), and    -   0.01 to 20 parts by weight, relative to 100 parts by weight of        the total of components (A-3) and (D), of (C) a second-order        modifier having a functional group which is reactive to the        functional group of the first-order modifier group (γ) of the        first-order modified polymer (A-3), wherein the second-order        modifier (C) is at least one member selected from the group        consisting of a functional monomer and a functional oligomer,        -   wherein the functional group-containing first-order modifier            group (γ) of the first-order modified polymer (A-3)            comprises at least one functional group represented by a            formula selected from the group consisting of the            above-mentioned formulae (a) to (m).

40. The modified polymer composition according to item 39 above, whereinthe thermoplastic resin in component (D) comprises at least one memberselected from the group consisting of a polyester resin, a polyamideresin, a polycarbonate resin, a polyurethane resin, a polyphenyleneether resin and a polyoxymethylene resin each of which contains at leastone functional group selected from the group consisting of an acidanhydride group, a carboxyl group, a hydroxyl group, an epoxy group, anamino group, a silanol group and an alkoxysilane group.

41. A crosslinked, modified polymer composition obtained by subjectingthe modified polymer composition of item 39 or 40 above to melt-kneadingin the presence of a vulcanizing agent.

42. An adhesive composition comprising:

-   -   100 parts by weight of (A-3) a first-order modified polymer        comprising:        -   (β) a base polymer which is unhydrogenated or at least            partially hydrogenated and which is at least one member            selected from the group consisting of the following polymers            (β-1) to (β-3):            -   (β-1) a conjugated diene polymer comprising conjugated                diene monomer units,            -   (β-2) a copolymer comprising conjugated diene monomer                units and vinyl aromatic hydrocarbon monomer units, the                copolymer having no or at least one polymer block (H) of                the vinyl aromatic hydrocarbon monomer units, wherein                the copolymer has a vinyl aromatic hydrocarbon block                ratio of from 0 to less than 50% by weight, the vinyl                aromatic hydrocarbon block ratio being defined as the                percent by weight of the vinyl aromatic hydrocarbon                monomer units contained in the at least one polymer                block (H) of the vinyl aromatic hydrocarbon monomer                units, based on the total weight of vinyl aromatic                hydrocarbon monomer units contained in the copolymer as                in the unhydrogenated state, and            -   (β-3) a vinyl aromatic hydrocarbon polymer comprising                vinyl aromatic hydrocarbon monomer units, and        -   (γ) a functional group-containing first-order modifier group            bonded to the base polymer (P),    -   20 to 400 parts by weight of (E) a tackifier, and    -   0.01 to 20 parts by weight of (C) a second-order modifier having        a functional group which is reactive to the functional group of        the first-order modifier group (γ) of the first-order modified        polymer (A-3), wherein the second-order modifier (C) is at least        one member selected from the group consisting of a functional        monomer and a functional oligomer,        -   wherein the functional group-containing first-order modifier            group (γ) of the first-order modified polymer (A-3)            comprises at least one functional group represented by a            formula selected from the group consisting of the            above-mentioned formulae (a) to (m).

43. An asphalt composition comprising:

-   -   0.5 to 50 parts by weight of (A-3) a first-order modified        polymer comprising:        -   (β) a base polymer which is unhydrogenated or at least            partially hydrogenated and which is at least one member            selected from the group consisting of the following polymers            (β-1) to (β-3):            -   (β-1) a conjugated diene polymer comprising conjugated                diene monomer units,            -   (β-2) a copolymer comprising conjugated diene monomer                units and vinyl aromatic hydrocarbon monomer units, the                copolymer having no or at least one polymer block (H) of                the vinyl aromatic hydrocarbon monomer units, wherein                the copolymer has a vinyl aromatic hydrocarbon block                ratio of from 0 to less than 50% by weight, the vinyl                aromatic hydrocarbon block ratio being defined as the                percent by weight of the vinyl aromatic hydrocarbon                monomer units contained in the at least one polymer                block (H) of the vinyl aromatic hydrocarbon monomer                units, based on the total weight of vinyl aromatic                hydrocarbon monomer units contained in the copolymer as                in the unhydrogenated state, and            -   (β-3) a vinyl aromatic hydrocarbon polymer comprising                vinyl aromatic hydrocarbon monomer units, and        -   (γ) a functional group-containing first-order modifier group            bonded to the base polymer (β),    -   100 parts by weight of (F) an asphalt, and    -   0.01 to 20 parts by weight of (C) a second-order modifier having        a functional group which is reactive to the functional group of        the first-order modifier group (γ) of the first-order modified        polymer (A-3), wherein the second-order modifier (C) is at least        one member selected from the group consisting of a functional        monomer and a functional oligomer,        -   wherein the functional group-containing first-order modifier            group (γ) of the first-order modified polymer (A-3)            comprises at least one functional group represented by a            formula selected from the group consisting of the            above-mentioned formulae (a) to (m).

44. A styrene resin composition obtained by subjecting a raw materialmixture to radical polymerization, the raw material mixture comprising:

-   -   2 to 30 parts by weight, relative to 100 parts by weight of the        total of components (A-3) and (G), of (A-3) a first-order        modified polymer comprising:        -   (β) a base polymer which is unhydrogenated or at least            partially hydrogenated and which is at least one member            selected from the group consisting of the following polymers            (β-1) to (β-3):            -   (β-1) a conjugated diene polymer comprising conjugated                diene monomer units,            -   (β-2) a copolymer comprising conjugated diene monomer                units and vinyl aromatic hydrocarbon monomer units, the                copolymer having no or at least one polymer block (H) of                the vinyl aromatic hydrocarbon monomer units, wherein                the copolymer has a vinyl aromatic hydrocarbon block                ratio of from 0 to less than 50% by weight, the vinyl                aromatic hydrocarbon block ratio being defined as the                percent by weight of the vinyl aromatic hydrocarbon                monomer units contained in the at least one polymer                block (H) of the vinyl aromatic hydrocarbon monomer                units, based on the total weight of vinyl aromatic                hydrocarbon monomer units contained in the copolymer as                in the unhydrogenated state, and            -   (β-3) a vinyl aromatic hydrocarbon polymer comprising                vinyl aromatic hydrocarbon monomer units, and        -   (γ) a functional group-containing first-order modifier group            bonded to the base polymer (β),    -   98 to 70 parts by weight, relative to 100 parts by weight of the        total of components (A-3) and (G), of (G) a vinyl aromatic        hydrocarbon monomer or a mixture of a vinyl aromatic hydrocarbon        monomer and a comonomer copolymerizable with the vinyl aromatic        hydrocarbon monomer, and    -   0.01 to 20 parts by weight, relative to 100 parts by weight of        the total of components (A-3) and (G), of (C) a second-order        modifier having a functional group which is reactive to the        functional group of the first-order modifier group (γ) of the        first-order modified polymer (A-3), wherein the second-order        modifier (C) is at least one member selected from the group        consisting of a functional monomer and a functional oligomer,        -   wherein the functional group-containing first-order modifier            group (γ) of the first-order modified polymer (A-3)            comprises at least one functional group represented by a            formula selected from the group consisting of the            above-mentioned formulae (a) to (m).

45. The styrene resin composition according to item 44 above, whereinthe raw material mixture further comprises 0.5 to 300 parts by weight,relative to 100 parts by weight of component (A-3), of (B) a reinforcingfiller.

46. The styrene resin composition according to item 45 above, whereinthe reinforcing filler (B) is at least one member selected from thegroup consisting of a silica inorganic filler, a metal oxide, a metalhydroxide and carbon.

Hereinbelow, the present invention is described in detail.

In the present invention, the monomer units of the polymer are named inaccordance with a nomenclature wherein the names of the originalmonomers from which the monomer units are derived are used with the term“monomer unit” attached thereto. For example, the term “vinyl aromatichydrocarbon monomer unit” means a monomer unit which is formed in apolymer obtained by the polymerization of the vinyl aromatic hydrocarbonmonomer. The vinyl aromatic hydrocarbon monomer unit has a molecularstructure wherein the two carbon atoms of a substituted ethylene groupderived from a substituted vinyl group respectively form linkages toadjacent vinyl aromatic hydrocarbon monomer units. Similarly, the term“conjugated diene monomer unit” means a monomer unit which is formed ina polymer obtained by the polymerization of the conjugated dienemonomer. The conjugated diene monomer unit has a molecular structurewherein the two carbon atoms of an olefin corresponding to theconjugated diene monomer respectively form linkages to adjacentconjugated diene monomer units.

The first-order modified, hydrogenated polymer of the present inventioncomprises:

-   -   (1) a hydrogenated polymer obtained by hydrogenating at least        one unhydrogenated polymer selected from the group consisting of        (1-A) a polymer comprising conjugated diene monomer units and        (1-B) a copolymer comprising conjugated diene monomer units and        vinyl aromatic hydrocarbon monomer units, the copolymer (1-B)        having no or at least one polymer block (H) of the vinyl        aromatic hydrocarbon monomer units, and    -   (2) a functional group-containing first-order modifier group        bonded to the hydrogenated polymer (1), wherein the functional        group-containing first-order modifier group comprises at least        one functional group selected from the group consisting of a        hydroxyl group, an epoxy group, an amino group, a silanol group        and an alkoxysilane group,    -   the first-order modified, hydrogenated polymer having the        following characteristics (i) to (iv):    -   (i) a content of the vinyl aromatic hydrocarbon monomer units of        from 0 to 60% by weight, based on the weight of the hydrogenated        polymer,    -   (ii) a vinyl aromatic hydrocarbon block ratio of from 0 to less        than 50% by weight, wherein the vinyl aromatic hydrocarbon block        ratio is defined as the percent by weight of the vinyl aromatic        hydrocarbon monomer units contained in the at least one polymer        block (H) of the vinyl aromatic hydrocarbon monomer units, based        on the total weight of vinyl aromatic hydrocarbon monomer units        contained in the copolymer (1-B),    -   (iii) a weight average molecular weight of from 20,000 to        2,000,000, and    -   (iv) a hydrogenation ratio of more than 70%, as measured with        respect to the double bonds in the conjugated diene monomer        units.

The functional group-containing first-order modifier group (2) of thefirst-order modified, hydrogenated polymer of the present inventioncomprises at least one functional group selected from the groupconsisting of a hydroxyl group, an epoxy group, an amino group, asilanol group and an alkoxysilane group. Preferably, the functionalgroup-containing first-order modifier group (2) comprises at least onefunctional group represented by a formula selected from the groupconsisting of the following formulae (a) to (m):

-   -   wherein, in the formulae (a) to (m):        -   N represents a nitrogen atom, Si represents a silicon atom,            O represents an oxygen atom, C represents a carbon atom, and            H represents a hydrogen atom,        -   each of R¹ to R⁴ independently represents a hydrogen atom or            a C₁-C₂₄ hydrocarbon group which optionally has at least one            functional group selected from the group consisting of a            hydroxyl group, an epoxy group, an amino group, a silanol            group and a C₁-C₂₄ alkoxysilane group,        -   each R⁵ independently represents a C₁-C₄₈ hydrocarbon group            and optionally, independently has at least one functional            group selected from the group consisting of a hydroxyl            group, an epoxy group, an amino group, a silanol group and a            C₁-C₂₄ alkoxysilane group,        -   each R⁶ independently represents a hydrogen atom or a C₁-C₈            alkyl group,        -   wherein each of R¹ to R⁵ optionally, independently has            bonded thereto at least one atom selected from the group            consisting of an oxygen atom, a nitrogen atom, a sulfur atom            and a silicon atom, the at least one atom being present in a            linkage other than a hydroxyl group, an epoxy group, an            amino group, a silanol group and an alkoxysilane group.

More preferably, the first-order modified, hydrogenated polymer of thepresent invention is a compound represented by a formula selected fromthe group consisting of the following formulae (I) to (V):

-   -   wherein:    -   A¹ represents a unit which is represented by any one of the        following formulae (a-1) and (b-1):    -   B¹ represents a unit which is represented by the following        formula (c-1):    -   C¹ represents a unit which is represented by any one of the        following formulae (d-1) and (e-1):    -   D¹ represents a unit which is represented by the following        formula (f-1):        —R⁸—NHR³,   (f-1)    -   E¹ represents a unit which is represented by the following        formula (g-1):        —R⁹—P¹, and (g-1)    -   F¹ represents a unit which is represented by any one of the        following formulae (h-1) to (j-1):    -   wherein, in the formulae (I) to (III) and (a-1) to (j-1):        -   N represents a nitrogen atom, Si represents a silicon atom,            O represents an oxygen atom, C represents a carbon atom, and            H represents a hydrogen atom,        -   P¹ represents the hydrogenated polymer (1),        -   R^(1a) represents a trivalent aliphatic C₁-C₄₈ hydrocarbon            group,        -   each of R^(1b), R⁴, R⁸ to R¹⁰ and R¹³ to R¹⁵ independently            represents a C₁-C₄₈ alkylene group,        -   each of R², R³ and R¹¹ independently represents a C₁-C₄₈            alkyl group, a C₆-C₄₈ aryl group, an alkylaryl group            comprised of C₁-C₄₈ alkyl and C₆-C₄₈ aryl, an aralkyl group            comprised of C₁-C₄₈ alkyl and C₆-C₄₈ aryl, or a C₃-C₄₈            cycloalkyl group,        -   wherein each of R^(1a), R^(1b), R³, R⁴, R⁸ to R¹⁰ and R¹³ to            R¹⁵ optionally, independently has at least one functional            group selected from the group consisting of a hydroxyl            group, an epoxy group, an amino group, a silanol group and a            C₁-C₂₄ alkoxysilane group,        -   each of R⁵ to R⁷ and R¹² independently represents a hydrogen            atom, a C₁-C₄₈ alkyl group, a C₆-C₄₈ aryl group, an            alkylaryl group comprised of C₁-C₄₈ alkyl and C₆-C₄₈ aryl,            an aralkyl group comprised of C₁-C₄₈ alkyl and C₆-C₄₈ aryl,            or a C₃-C₄₈ cycloalkyl group,        -   wherein each of R^(1a), R^(1b), R² to R⁴ and R⁸ to R¹⁵            optionally, independently has bonded thereto at least one            atom selected from the group consisting of an oxygen atom, a            nitrogen atom, a sulfur atom and a silicon atom, the at            least one atom being present in a linkage other than a            hydroxyl group, an epoxy group, an amino group, a silanol            group and an alkoxysilane group, and        -   each of k, l, m and o is independently an integer of 0 or            more, provided that both k and l are not simultaneously 0,            and n is an integer of 1 or more.

The hydrogenated polymer (1) which is a precursor of the first-ordermodified, hydrogenated polymer of the present invention (hereinafter,frequently referred to as “a base polymer which is the hydrogenatedpolymer (1)”) is obtained by hydrogenating at least one unhydrogenatedpolymer selected from the group consisting of (1-A) a polymer comprisingconjugated diene monomer units and (1-B) a copolymer comprisingconjugated diene monomer units and vinyl aromatic hydrocarbon monomerunits, the copolymer (1-B) having no or at least one polymer block (H)of the vinyl aromatic hydrocarbon monomer units.

In the present invention, the first-order modified, hydrogenated polymerhas characteristic (i). Specifically, the content of the vinyl aromatichydrocarbon monomer units is from 0 to 60% by weight, preferably 5 to50% by weight, more preferably 10 to 35% by weight, based on the weightof the hydrogenated polymer. When the content of the vinyl aromatichydrocarbon monomer units is in the range of from 0 to 60% by weight,such a polymer is advantageous for preparing compositions havingexcellent properties. From the viewpoint of obtaining a compositionhaving excellent mechanical strength and processability, it is preferredthat the content of the vinyl aromatic hydrocarbon monomer units is inthe range of from 10 to 35% by weight, based on the weight of thehydrogenated polymer.

The first-order modified, hydrogenated polymer of the present inventionhas characteristic (ii). Specifically, the vinyl aromatic hydrocarbonblock ratio is from 0 to less than 50% by weight, preferably 5 to 40% byweight, more preferably 5 to 30% by weight, wherein the vinyl aromatichydrocarbon block ratio is defined as the percent by weight of the vinylaromatic hydrocarbon monomer units contained in the at least one polymerblock (H) of the vinyl aromatic hydrocarbon monomer units, based on thetotal weight of vinyl aromatic hydrocarbon monomer units contained inthe copolymer (1-B). When the first-order modified, hydrogenated polymerhas at least one polymer block (H), the vinyl aromatic hydrocarbon blockratio is not less than 5% by weight. When a composition is preparedusing a first-order modified, hydrogenated polymer having a vinylaromatic hydrocarbon block ratio of less than 50% by weight, theprepared composition exhibits excellent flexibility.

In the present invention, the vinyl aromatic hydrocarbon block ratio canbe measured, for example, by the following method. The weight of thevinyl aromatic hydrocarbon polymer block (H) (i.e., the weight of thevinyl aromatic hydrocarbon monomer units contained in the polymer block(H)) is obtained by a method in which the unhydrogenated copolymer issubjected to oxidative degradation in the presence of osmium tetraoxideas a catalyst using tert-butyl hydroperoxide (i.e., method described inI. M. KOLTHOFF et al., J. Polym. Sci. 1, 429 (1946)). Using the obtainedweight of the vinyl aromatic hydrocarbon polymer block (H), the vinylaromatic hydrocarbon block ratio of the hydrogenated copolymer iscalculated by the following formula, with the proviso that, among thepolymer chains (formed by the oxidative degradation) corresponding tothe vinyl aromatic hydrocarbon polymer blocks (H), the polymer chainshaving an average polymerization degree of 30 or less are not taken intoconsideration in the measurement of the vinyl aromatic hydrocarbon blockratio.

The vinyl aromatic hydrocarbon block ratio (% by weight)=(weight of thevinyl aromatic hydrocarbon monomer units contained in the polymer block(H) in the copolymer prior to the hydrogenation/total weight of vinylaromatic hydrocarbon monomer units contained in the copolymer prior tothe hydrogenation)×100.

In the present invention, the microstructure (including the amounts of acis bond, a trans bond and a vinyl bond) of the conjugated diene monomerunits in the polymer prior to the hydrogenation (unhydrogenated polymer)can be appropriately controlled by using the below-described polarcompound and the like. When 1,3-butadiene (which is addition-polymerizedthrough a cis-1,4 bond, a trans-1,4 bond or a 1,2-vinyl bond) is used asthe conjugated diene monomer, the 1,2-vinyl bond content is generally inthe range of from 5 to 80 mol %, preferably from 10 to 60 mol %, basedon the total molar amount of the cis-1,4 bond, trans-1,4 bond and1,2-vinyl bond. When isoprene or a combination of 1,3-butadiene andisoprene is used as the conjugated diene monomer, it is preferred thatthe total content of the 1,2-vinyl bond and 3,4-vinyl bond is in therange of from 3 to 75 mol %, more advantageously from 5 to 60%, based onthe total molar amount of the cis-1,4 bond, trans-1,4 bond, 1,2-vinylbond and 3,4-vinyl bond. In the present invention, the total content ofthe 1,2-vinyl bond and 3,4-vinyl bond (or the content of the 1,2-vinylbond in the case where 1,3-butadiene is used as the conjugated dienemonomer) is defined as the vinyl bond content.

In the unhydrogenated polymer, the vinyl bonds may be uniformlydistributed or may be distributed in a tapered configuration. Further,the polymer block may have a plurality of segments having differentvinyl bond contents. The difference in the vinyl bond distribution canbe controlled by changing the polymerization conditions, such as thetype and amount of the vinyl bond formation-controlling agent andpolymerization reaction temperature. For example, when the type andamount of the vinyl bond formation-controlling agent (such as a tertiaryamine or an ether compound) are not changed during the polymerization ofa conjugated diene monomer or the copolymerization of a conjugated dienemonomer and a vinyl aromatic hydrocarbon monomer, the amount of thevinyl bonds formed in the resultant polymer is influenced only by thepolymerization reaction temperature. Therefore, in this case, when thepolymerization reaction is conducted at a constant polymerizationreaction temperature, the vinyl bonds are uniformly distributed in theresultant polymer. On the other hand, when the polymerization isconducted while elevating the polymerization reaction temperature, theresultant polymer has a non-uniform distribution with respect to thevinyl bonds, wherein a portion of the polymer which is formed at anearly stage of the polymerization (where the polymerization reactiontemperature is low) has a high vinyl bond content and a portion of thepolymer which is formed at a late stage of the polymerization (where thepolymerization reaction temperature is high) has a low vinyl bondcontent. The below-mentioned hydrogenated polymer having a specificstructure is obtained by hydrogenating the polymer having such astructure.

The first-order modified, hydrogenated polymer has characteristic (iii).Specifically, the weight average molecular weight is from 20,000 to2,000,000, preferably 50,000 to 1,500,000, more preferably 100,000 to1,000,000. The weight average molecular weight can be measured by gelpermeation chromatography (GPC) using a calibration curve obtained usinga chromatogram of standard polystyrene samples commercially available(the calibration curve is obtained by the use of the peak molecularweights of the standard polystyrene samples).

In the present invention, the molecular weight distribution of thefirst-order modified, hydrogenated polymer is preferably in the range offrom 1.05 to 5.0. As explained below, the preferred molecular weightdistribution varies depending on the difference between the maximumvalue and minimum value of the vinyl bond content and the hydrogenationratio of the first-order modified, hydrogenated polymer. For example,when the difference between the maximum value and minimum value of thevinyl bond content is less than 10% by weight, the molecular weightdistribution is preferably less than 1.5. When not only the differencebetween the maximum value and minimum value of the vinyl bond content isless than 10% by weight, but also the hydrogenation ratio is more than70% and less than 85%, the molecular weight distribution is preferablyin the range of from 1.5 to 5.0. The molecular weight distribution canalso be obtained by GPC as in the case of the measurement of the weightaverage molecular weight.

The first-order modified, hydrogenated polymer of the present inventionis a hydrogenated polymer obtained by hydrogenating at least oneunhydrogenated polymer selected from the group consisting of a polymercomprising conjugated diene monomer units and a copolymer comprisingconjugated diene monomer units and vinyl aromatic hydrocarbon monomerunits. The first-order modified, hydrogenated polymer has characteristic(iv). Specifically, the hydrogenation ratio is more than 70%, preferably75% or more, more preferably 80% or more, as measured with respect tothe double bonds in the conjugated diene monomer units. For producing arubbery composition having excellent weatherability, it is especiallypreferred that the hydrogenation ratio of the first-order modified,hydrogenated polymer is 80% or more, more preferably 85% or more, stillmore preferably 90% or more.

However, as explained below, depending on the relationship between thevinyl bond content and the molecular weight distribution of thefirst-order modified, hydrogenated polymer, there are cases where apreferred hydrogenation ratio is in the range of from 70% to less than85%. Further, from the viewpoint of obtaining a vulcanized compositionwhich exhibits excellent properties imparted by vulcanization, it isrecommended that the hydrogenation ratio is not more than 98%,preferably not more than 95%, still more preferably not more than 90%.Further, in the first-order modified, hydrogenated polymer of thepresent invention, from the viewpoint of obtaining a composition havingexcellent heat stability, it is recommended that the hydrogenation ratiois not less than 85%, preferably not less than 90%, still morepreferably not less than 95%. There is no particular limitation withrespect to the hydrogenation ratio as measured with respect to thearomatic double bonds in the vinyl aromatic hydrocarbon monomer units ofthe first-order modified, hydrogenated polymer. However, it isrecommended that the hydrogenation ratio is preferably not more than50%, more preferably not more than 30%, still more preferably not morethan 20%.

Exemplified below are the especially preferred examples of thefirst-order modified, hydrogenated polymer of the present inventionwhich satisfy the above-mentioned characteristics (i) to (iv):

-   -   1) A first-order modified, hydrogenated polymer having a        characteristic wherein the difference between the maximum value        and minimum value of the vinyl bond content is 10% by weight or        more;    -   2) A first-order modified, hydrogenated polymer having        characteristics wherein the difference between the maximum value        and minimum value of the vinyl bond content is less than 10% by        weight, and the molecular weight distribution is less than 1.55;    -   3) A first-order modified, hydrogenated polymer having        characteristics wherein the difference between the maximum value        and minimum value of the vinyl bond content is less than 10% by        weight, the molecular weight distribution is in the range of        from 1.55 to 5.0, and the hydrogenation ratio is more than 70%        and less than 85%, as measured with respect to the double bonds        in the conjugated diene monomer units;    -   4) A first-order modified, hydrogenated polymer having a        characteristic wherein the molecular weight and the number of        carbon atoms of the terminal methyl group, both determined by        GPC/FT-IR analysis, satisfy the relationship defined by the        following formula {circle over (4)}:        V _(a) −V _(b)<0.03V _(c)   {circle over (1)}        wherein V is defined as the number of carbon atoms of a terminal        methyl group of a polymer chain, relative to 1,000 carbon atoms        contained in the polymer chain; V_(a) is defined as the V value        of a polymer chain having a molecular weight which is twice the        peak top molecular weight of the first-order modified,        hydrogenated polymer; V_(b) is defined as the V value of a        polymer chain having a molecular weight which is ½ of the peak        top molecular weight of the first-order modified, hydrogenated        polymer; and V_(c) is the V value of a polymer chain having the        peak top molecular weight of the first-order modified,        hydrogenated polymer;    -   5) A first-order modified, hydrogenated polymer having        characteristics wherein the average vinyl bond content is either        less than 20% by weight or 50% by weight or more, and the        molecular weight and the number of carbon atoms of the terminal        methyl group, both determined by GPC/FT-IR analysis, satisfy the        relationship defined by the following formula {circle over (2)}:        V _(a) −V _(b)≧0.03V _(c)   {circle over (2)}        wherein V_(a), V_(b) and V_(c) are as defined for formula        {circle over (1)} above; and    -   6) A first-order modified, hydrogenated polymer having        characteristics wherein the average vinyl bond content is 20% by        weight or more and less than 50% by weight, the hydrogenation        ratio is more than 70% and less than 85%, as measured with        respect to the double bonds in the conjugated diene monomer        units, and the molecular weight and the number of carbon atoms        of the terminal methyl group, both determined by GPC/FT-IR        analysis, satisfy the relationship defined by formula {circle        over (2)} above.

GPC/FT-IR is an apparatus in which an FT-IR (Fourier Transform Infrared)Spectrometer is used as detector for a GPC (gel permeationchromatography) and this apparatus enables the determination of themicrostuctures of a substance which has been fractionated based on themolecular weight. The number of carbon atoms of a terminal methyl groupcan be determined from the ratio I(—CH₃)/I(—CH₂—), which is the ratio ofthe absorbance I(—CH₃) <absorption wave number: 2960 cm⁻¹> ascribed tothe methyl group to the absorbance I(—CH₂—) <absorption wave number:2925 cm⁻¹> ascribed to the methylene group. This method is described in,for example, “NICOLET FT-IR CUSTOMER NEWSLETTER”, Vol. 2, No. 2, 1994.

The above-exemplified preferred first-order modified, hydrogenatedpolymer can be obtained as follows. A conjugated diene monomer solely ora combination of a conjugated diene monomer and a vinyl aromatichydrocarbon monomer are subjected to continuous polymerization reactionin the presence of an organic alkali metal compound as a polymerizationinitiator and a vinyl bond formation-controlling agent to thereby obtaina base polymer having a living terminal. Then, a functionalgroup-containing first-order modifier is addition-bonded to the livingterminal of the base polymer to obtain a first-order modified,unhydrogenated polymer, followed by hydrogenation, to thereby obtain afirst-order modified, hydrogenated polymer. In this method, in the stepof continuously polymerizing a conjugated diene monomer solely or acombination of a conjugated diene monomer and a vinyl aromatichydrocarbon monomer, the amount of the vinyl bond formation-controllingagent (relative to the amount of the organic alkali metal compound) maybe varied. In the present invention, the “amount of the vinyl bondformation-controlling agent, relative to the amount of the organicalkali metal compound” is the ratio of the total amount of the vinylbond formation-controlling agent present in the polymerization reactionsystem to the amount of the organic alkali metal compound continuouslyfed to the reaction system. Specifically, the first-order modified,hydrogenated polymer can be produced using a reaction system comprisingtwo or more polymerization reactors which are connected in series. Anorganic alkali metal compound, a conjugated diene monomer solely or acombination of a conjugated diene monomer and a vinyl aromatichydrocarbon monomer, and optionally a vinyl bond formation-controllingagent are continuously fed to the first polymerization reactor and acontinuous polymerization is performed in the reactor to obtain areaction mixture containing a polymer of the conjugated diene monomer ora copolymer of the conjugated diene monomer and the vinyl aromatichydrocarbon monomer. Subsequently, the obtained reaction mixture and aconjugated diene monomer solely or a combination of a conjugated dienemonomer and a vinyl aromatic hydrocarbon monomer are continuously fed toa subsequent reactor or reactors, while feeding a vinylbond-formation-controlling agent to at least one of the subsequentreactor(s), to thereby effect further polymerization and obtain a basepolymer having a living terminal. Then, a functional group-containingfirst-order modifier is addition-bonded to the living terminal of thebase polymer to obtain a first-order modified polymer, followed byhydrogenation of the obtained first-order modified polymer.

For example, the first-order modified, hydrogenated polymer can beproduced using a reaction system comprising two polymerization reactorswhich are connected in series. The organic alkali metal compound, aconjugated diene monomer solely or a combination of a conjugated dienemonomer and a vinyl aromatic hydrocarbon monomer, and optionally a vinylbond formation-controlling agent are continuously fed to the firstpolymerization reactor and continuously polymerized therein to therebyobtain a reaction mixture containing a polymer of a conjugated dienemonomer or a copolymer of a conjugated diene monomer and a vinylaromatic hydrocarbon monomer. The obtained reaction mixture and aconjugated diene monomer solely or a combination of a conjugated dienemonomer and a vinyl aromatic hydrocarbon monomer are continuously fed tothe second reactor together with a vinyl bond formation-controllingagent, to thereby effect a further polymerization and obtain a basepolymer having a living terminal. Then, a functional group-containingfirst-order modifier is addition-bonded to the living terminal of thebase polymer to obtain a first-order modified polymer. Subsequently,hydrogenation of the obtained first-order modified polymer is performedto obtain a first-order modified, hydrogenated polymer. In this method,the amount of the vinyl bond formation-controlling agent fed to thefirst and second polymerization reactors must be controlled so that themolecular weight and the number of carbon atoms of the terminal methylgroup (both determined by the GPC/FT-IR analysis) of the producedfirst-order modified, hydrogenated polymer satisfy the specificrelationship defined in the present invention.

In another aspect of the present invention, there is provided asecond-order modified polymer comprising:

-   -   (β) a base polymer, and    -   (δ) a functional group-containing modifier group bonded to the        base polymer (β),    -   wherein the second-order modified polymer is obtained by        reacting a second-order modifier with a first-order modified        polymer comprising (β) a base polymer and (γ) a functional        group-containing first-order modifier group bonded to the base        polymer (β) to thereby form (δ) a functional group-containing        modifier group, wherein the second-order modifier has a        functional group which is reactive to the functional group of        the first-order modifier group (γ) of the first-order modified        polymer, and wherein the second-order modifier is used in an        amount of 0.3 to 10 moles, relative to one equivalent of the        functional group of the first-order modifier group (γ) of the        first-order modified polymer,    -   the second-order modifier being at least one member selected        from the group consisting of a functional monomer and a        functional oligomer,        -   wherein the base polymer (β) of the first-order modified            polymer is unhydrogenated or at least partially hydrogenated            and is at least one member selected from the group            consisting of the following polymers (β-1) to (β-3):            -   (β-1) a conjugated diene polymer comprising conjugated                diene monomer units,            -   (β-2) a copolymer comprising conjugated diene monomer                units and vinyl aromatic hydrocarbon monomer units, the                copolymer having no or at least one polymer block (H) of                the vinyl aromatic hydrocarbon monomer units, wherein                the copolymer has a vinyl aromatic hydrocarbon block                ratio of from 0 to less than 50% by weight, the vinyl                aromatic hydrocarbon block ratio being defined as the                percent by weight of the vinyl aromatic hydrocarbon                monomer units contained in the at least one polymer                block (H) of the vinyl aromatic hydrocarbon monomer                units, based on the total weight of vinyl aromatic                hydrocarbon monomer units contained in the copolymer as                in the unhydrogenated state, and            -   (β-3) a vinyl aromatic hydrocarbon polymer comprising                vinyl aromatic hydrocarbon monomer units, and        -   wherein the functional group-containing first-order modifier            group (y) of the first-order modified polymer comprises at            least one functional group represented by a formula selected            from the group consisting of the above-mentioned            formulae (a) to (m).

The base polymer (β) of the second-order modified polymer of the presentinvention is at least one member selected from the group consisting ofpolymers (β-1) to (β-3), that is, a conjugated diene polymer (β-1)comprising conjugated diene monomer units, a vinyl aromatic hydrocarbonpolymer (β-3) comprising vinyl aromatic hydrocarbon monomer units, and acopolymer (β-2) comprising conjugated diene monomer units and vinylaromatic hydrocarbon monomer units. In general, copolymer (β-2) abovehas a content of the vinyl aromatic hydrocarbon monomer units of from 5to 95% by weight, preferably 10 to 90% by weight, more preferably 15 to85% by weight. With respect to the base polymer (β), a polymer havingthe content of the vinyl aromatic hydrocarbon monomer units of less than5% by weight is defined as a conjugated diene polymer, and a polymerhaving the content of the vinyl aromatic hydrocarbon monomer units ofmore than 95% by weight is defined as a vinyl aromatic hydrocarbonpolymer.

When the second-order modified polymer is an unhydrogenated polymer, thecontent of the vinyl aromatic hydrocarbon monomer units can be measuredwith respect to either the base polymer (β) prior to the first-ordermodification or the first-order modified polymer prior to thesecond-order modification (hereinafter, frequently referred to as a“precursory first-modified polymer”). When the second-order modifiedpolymer is a hydrogenated or partially hydrogenated polymer, the contentof the vinyl aromatic hydrocarbon monomer units can be measured withrespect to either a base polymer (β) prior to the first-ordermodification or a precursory first-order modified polymer prior to thehydrogenation.

In the second-order modified polymer of the present invention, when thebase polymer (β) is a copolymer (β-2), the copolymer (β-2) comprisesconjugated diene monomer units and vinyl aromatic hydrocarbon monomerunits and has no or at least one polymer block (H) of the vinyl aromatichydrocarbon monomer units. The vinyl aromatic hydrocarbon block ratio isless than 50% by weight, preferably 40% by weight or less, morepreferably 20% by weight or less, the vinyl aromatic hydrocarbon blockratio being defined as the percent by weight of the vinyl aromatichydrocarbon monomer units contained in the at least one polymer block(H) of the vinyl aromatic hydrocarbon monomer units, based on the totalweight of vinyl aromatic hydrocarbon monomer units contained in thecopolymer as in the unhydrogenated state. When a second-order modifiedpolymer is produced using copolymer (β-2) having a vinyl aromatichydrocarbon block ratio of less than 50% by weight, a compositioncontaining such a second-order modified polymer exhibits excellentflexibility.

The base polymer (β) of the first-order modified polymer used forproducing the second-order modified polymer of the present invention isunhydrogenated or at least partially hydrogenated. When the base polymer(β) is hydrogenated, there is no particular limitation with respect tothe hydrogenation ratio as measured with respect to the unsaturateddouble bonds in the conjugated diene monomer units, and thehydrogenation ratio can be appropriately controlled to a desired level.It is preferred that the hydrogenation ratio is more than 70%, morepreferably 75% or more, still more preferably 85% or more, mostpreferably 90% or more, as measured with respect to the unsaturateddouble bonds in the conjugated diene monomer units. When the basepolymer (β) is partially hydrogenated, it is preferred that thehydrogenation ratio is 10 to 7.0%, more advantageously 15 to 65%, mostadvantageously 20 to 60%, as measured with respect to the unsaturateddouble bonds in the conjugated diene monomer units. From the viewpointof obtaining a vulcanized composition having excellent propertiesimparted by vulcanization, it is recommended that the hydrogenationratio is not more than 98%, preferably not more than 95%, still morepreferably not more than 90%.

In the present invention, when the base polymer (β) is a hydrogenatedpolymer, from the viewpoint of obtaining a polymer composition havingexcellent heat stability, it is recommended that the hydrogenation ratioas measured with respect to the vinyl bonds in the conjugated dienemonomer units of the unhydrogenated polymer is preferably 85% or more,more preferably 90% or more, still more preferably 95% or more. Herein,the hydrogenation ratio with respect to the vinyl bonds is the ratio ofhydrogenated vinyl bonds to the vinyl bonds in the conjugated dienemonomer units of the unhydrogenated polymer. There is no particularlimitation with respect to the hydrogenation ratio as measured withrespect to the aromatic double bonds in the vinyl aromatic hydrocarbonmonomer units of the polymer. However, it is recommended that thehydrogenation ratio is preferably 50% or less, more preferably 30% orless, still more preferably 20% or less. The hydrogenation ratio can bemeasured by a method using a nuclear magnetic resonance (NMR) apparatus.

With respect to the weight average molecular weight of the second-ordermodified polymer of the present invention, there is no particularlimitation. However, from the viewpoint of improving the mechanicalstrength of the polymer composition, it is preferred that thesecond-order modified polymer of the present invention has a weightaverage molecular weight of 20,000 or more. Further, from the viewpointof improving the processability of the polymer composition, it ispreferred that the second-order modified polymer has a weight averagemolecular weight of 2,000,000 or less. The weight average molecularweight is more preferably from 50,000 to 1,500,000, still morepreferably from 100,000 to 1,000,000. The molecular weight distributionof the second-order modified polymer is preferably from 1.05 to 6.0,more preferably 1.1 to 6.0, still more preferably 1.55 to 5.0, and mostpreferably from 1.6 to 4.0.

With respect to the structure of the base polymer (β) of the first-ordermodified polymer (precursory first-order modified polymer) which is aprecursor of the second-order modified polymer of the present invention,there is no particular limitation, and the base polymer (β) may have anystructure. For example, when the base polymer is a conjugated dienepolymer comprising conjugated diene monomer units or a copolymercomprising conjugated diene monomer units and vinyl aromatic hydrocarbonmonomer units, use can be made of a polymer having a structurerepresented by a formula selected from the group consisting of thebelow-mentioned formulae (p1) to (p7). Further, with respect to thefirst-order modified, hydrogenated polymer of the present invention, ahydrogenated polymer having a structure selected from the groupconsisting of the structures represented by the below-mentioned formulae(p1) to (p7) can be used as the hydrogenated polymer (1) (namely a basepolymer), as long as the structure satisfies all of the above-mentionedcharacteristics (i) to (iv). (It should be noted that the base polymer(β) of the precursory first-order modified polymer is unhydrogenated orat least partially hydrogenated.)(B)_(n)—X and/or (S)_(n)—X,   (p1)(B—S)_(n)—X and/or (S—B)_(n)—X,   (p2)[(B—S)]_(m)—X and/or [(S—B)_(n)]_(m)—X,   (p3)(S—H)_(n)—X and/or [(S—H)_(n)]_(m)—X,   (p4)(B—H)_(n)—X and/or [(B—H)_(n)]_(m)—X,   (p5)(B—S—H)_(n)—X and/or [(B—S—H)_(n)]_(m)—X and   (p6)(S—B—H)_(n)—X and/or [(S—B—H)_(n)]_(m)—X   (p7)

-   -   wherein each B represents a polymer block of conjugated diene        monomer units, each S independently represents a random        copolymer block comprised of conjugated diene monomer units and        vinyl aromatic hydrocarbon monomer units, each H independently        represents a polymer block of vinyl aromatic hydrocarbon monomer        units, n represents an integer of 1 or more, m represents an        integer of 2 or more, preferably in the range of from 2 to 10,        and each X represents a functional group-containing first-order        modifier group.

With respect to the structures of the above formulae (p1) to (p7), thevinyl bonds may be uniformly distributed in the conjugated dienepolymer, a random copolymer comprising conjugated diene monomer units, apolymer block of conjugated diene monomer units and a random copolymerblock comprising conjugated diene monomer units. Alternatively, theabove-mentioned polymers and polymer blocks may have a plurality ofsegments having different vinyl bond contents. Further, the vinylaromatic hydrocarbon monomer units may be uniformly distributed or maybe distributed in a tapered configuration in the random copolymer andthe random copolymer block S. The random copolymer and the randomcopolymer block S may have a plurality of segments in which the vinylaromatic hydrocarbon monomer units are uniformly distributed and/or mayhave a plurality of segments in which the vinyl aromatic hydrocarbonmonomer units are distributed in a tapered configuration.

In the present invention, the content of the vinyl aromatic hydrocarbonmonomer units can be measured by means of an UV spectrometer, aninfrared spectrometer, a nuclear magnetic resonance (NMR) apparatus andthe like. The vinyl aromatic hydrocarbon block ratio can be measured bythe above-mentioned method of KOLTHOFF. With respect to the polymerprior to the hydrogenation (unhydrogenated polymer), the vinyl bondcontent of the conjugated diene monomer units can be measured by amethod (Hampton method) using an infrared spectrometer or a method usinga nuclear magnetic resonance (NMR) apparatus. The hydrogenation ratio ofthe first-order modified hydrogenated polymer can be measured by meansof an infrared spectrometer or a nuclear magnetic resonance (NMR)apparatus.

The first-order modified, hydrogenated polymer of the present inventionand the precursory first-order modified polymer which is the precursorof the second-order modified polymer of the present invention, can beproduced in substantially the same manner. The methods for producingthese polymers are explained in detail below.

Firstly, the hydrogenated polymer (1) which is the base polymer of thefirst-order modified, hydrogenated polymer or the base polymer (β) ofthe precursory first-order modified polymer is produced. The conjugateddiene monomer used in the present invention is a diolefin having a pairof conjugated double bonds. Specific examples of conjugated dienemonomers include 1,3-butadiene, 2-methyl-1,3-butadiene(isoprene),2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene and1,3-hexadiene. Of these, especially preferred are 1,3-butadiene andisoprene. The above conjugated diene monomers can be used individuallyor in combination. Examples of vinyl aromatic hydrocarbon monomersinclude styrene, α-methylstyrene, p-methylstyrene, divinylbenzene,1,1-diphenylethylene, N,N-dimethyl-p-aminoethylstyrene andN,N-diethyl-p-aminoethylstyrene. These vinyl aromatic hydrocarbonmonomers can be used individually or in combination.

The polymer prior to the hydrogenation (unhydrogenated polymer) can beproduced, for example, by a living anionic polymerization conducted in ahydrocarbon solvent using a polymerization initiator, such as an organicalkali metal compound. Examples of hydrocarbon solvents includealiphatic hydrocarbons, such as n-butane, isobutane, n-pentane,n-hexane, n-heptane and n-octane; alicyclic hydrocarbons, such asmethylcyclopentane, cyclohexane, cycloheptane and methylcycloheptane;and aromatic hydrocarbons, such as benzene, toluene, xylene andethylbenzene.

As the polymerization initiator, it is possible to use aliphatichydrocarbon-alkali metal compounds, aromatic hydrocarbon-alkali metalcompounds and organic amino-alkali metal compounds, which are generallyknown to have a living anionic polymerization activity with respect to aconjugated diene and a vinyl aromatic hydrocarbon compound. Examples ofalkali metals include lithium, sodium and potassium.

Examples of organic alkali metal compounds include lithium compoundshaving at least one lithium atom in a molecule of C₁-C₂₀ aliphatic oraromatic hydrocarbons (such as a dilithium compound, a trilithiumcompound and a tetralithium compound). Specific examples of lithiumcompounds include n-propyllithium, n-butyllithium, sec-butyllithium,tert-butyllithium, n-pentyllithium, n-hexyllithium, benzyllithium,phenyl-lithium, tolyllithium, a reaction product of diisopropenylbenzene and sec-butyllithium, and a reaction product obtained byreacting divinyl benzene, secbutyllithium and a small amount of1,3-butadiene. Further, it is also possible to use any of the organicalkali metal compounds described in U.S. Pat. No. 5,708,092, GB PatentNo. 2,241,239 and U.S. Pat. No. 5,527,753. These organic alkali metalcompounds can be used individually or in combination.

In the present invention, when the copolymerization of a conjugateddiene monomer and a vinyl aromatic hydrocarbon monomer is performed inthe presence of the organic alkali metal compound as a polymerizationinitiator, it is possible to use a tertiary amine compound or an ethercompound as a vinyl bond formation-controlling agent, which is used forcontrolling the amount of vinyl bonds (i.e., a 1,2-vinyl bond and a3,4-vinyl bond) formed by the conjugated diene monomers, and forcontrolling the occurrence of a random copolymerization of a conjugateddiene monomer and a vinyl aromatic hydrocarbon monomer. As the tertiaryamine compound, it is possible to use a compound represented by theformula:R¹R²R³N

-   -   wherein each of R¹, R² and R³ independently represents a C₁-C₂₀        hydrocarbon group or a C₁₋C₂₀ hydrocarbon group substituted with        a tertiary amino group.

Specific examples of tertiary amine compounds include trimethylamine,triethylamine, tributylamine, N,N-di-methylaniline, N-ethylpiperidine,N-methylpyrrolidine, N,N,N′,N′-tetramethylethylenediamine,N,N,N′,N′-tetraethylethylenediamine, 1,2-dipiperidinoethane,tri-methylaminoethylpiperazine,N,N,N′,N″,N″-pentamethyl-ethylenetriamine andN,N′-dioctyl-p-phenylenediamine.

As the above-mentioned ether compound, it is possible to use a linearether compound and a cyclic ether compound. Examples of linear ethercompounds include dimethyl ether; diethyl ether; diphenyl ether;ethylene glycol dialkyl ethers, such as ethylene glycol dimethyl ether,ethylene glycol diethyl ether and ethylene glycol dibutyl ether; anddiethylene glycol dialkyl ethers, such as diethylene glycol dimethylether, diethylene glycol diethyl ether and diethylene glycol dibutylether. Examples of cyclic ether compounds include tetrahydrofuran,dioxane, 2,5-dimethyloxolane, 2,2,5,5-tetramethyloxolane,2,2-bis(2-oxolanyl)propane and an alkyl ether of a furfuryl alcohol.

In the present invention, the polymerization of a conjugate dienemonomer, the copolymerization of a conjugated diene monomer and a vinylaromatic hydrocarbon monomer and the polymerization of a vinyl aromatichydrocarbon monomer in the presence of the organic alkali metal compoundas a polymerization initiator can be conducted either in a batchwisemanner or in a continuous manner. Further, the polymerization orcopolymerization may be conducted in a manner wherein a batchwiseoperation and a continuous operation are used in combination. Thereaction temperature for the polymerization or copolymerization isgenerally in the range of from 0 to 180° C., preferably from 30 to 150°C. The reaction time for the polymerization or copolymerization variesdepending on other conditions, but is generally within 48 hours,preferably in the range of from 0.1 to 10 hours. It is preferred thatthe atmosphere of the polymerization or copolymerization reaction systemis an atmosphere of an inert gas, such as nitrogen gas. With respect tothe polymerization reaction pressure, there is no particular limitationso long as the pressure is sufficient for maintaining each of themonomer(s) and the solvent in a liquid state at a reaction temperaturein the above-mentioned range. Further, care must be taken to prevent theintrusion of impurities (such as water, oxygen and carbon dioxide),which deactivate the catalyst and/or the living polymer, into thepolymerization reaction system.

Next, a first-order modifier is addition-bonded to the living terminalof the base polymer produced in the above-mentioned manner, to therebyobtain a first-order modified polymer having a functionalgroup-containing first-order modifier bonded to the living terminal ofthe base polymer. The thus obtained first-order modified polymer can behydrogenated to obtain a first-order modified, hydrogenated polymer. Thefirst-order modified, hydrogenated polymer of the present invention hasa functional group-containing first-order modifier group (2) comprisingat least one functional group selected from the group consisting of ahydroxyl group, an epoxy group, an amino group, a silanol group and analkoxysilane group; and the precursory first-order modified polymer usedfor producing the second-order modified polymer of the present inventionhas the functional group-containing first-order modifier group (γ)comprising at least one functional group represented by a formulaselected from the group consisting of the above-mentioned formulae (a)to (m). As in the case of a preferred example of the first-ordermodified, hydrogenated polymer of the present invention, the first-ordermodified polymer which is preferred for use as a precursory first-ordermodified polymer is the first-order modified, hydrogenated polymerrepresented by a formula selected from the group consisting of theabove-mentioned formulae (I) to (V).

As another method for producing the first-order modified polymer, therecan be mentioned a method in which an organic alkali metal compound,such as an organolithium compound, is addition-bonded to a base polymerwhich does not have a living terminal (this addition reaction is called“metalation reaction”), followed by the addition of a first-ordermodifier to the base polymer. In this method, the base polymer may behydrogenated before the metalation reaction and the subsequent additionof the first-order modifier. When the base polymer is reacted with thefirst-order modifier, it is possible that a hydroxyl group, an aminogroup and the like, which are contained in the resultant modifier groupof the modified polymer, are converted to organic metal salts thereof,depending on the type of modifier. In such case, the organic metal saltscan be reconverted back to functional groups (i.e., a hydroxyl group, anamino group and the like) by reacting the organic metal salts with anactive hydrogen-containing compound, such as water, an alcohol and thelike.

In the present invention, a first-order modified polymer obtained by theaddition of the first-order modifier to the living terminal of the basepolymer, may contain an unmodified polymer fraction. However, withrespect to the first-order modified, hydrogenated polymer and theprecursory first-order modified polymer used in the composition of thepresent invention, it is recommended that the amount of the modifiedpolymer fraction in the modified polymer is preferably more than 30% byweight, more preferably 40% by weight or more, still more preferably 50%by weight or more, based on the weight of the modified polymer. Themaximum amount of the modified polymer fraction is 100% by weight. Whenthe amount of the modified polymer fraction is large, the interactionsare effectively caused to occur between such a modified polymer and areinforcing filler. The amount of the modified polymer fraction can bedetermined by a chromatography which is capable of separating themodified polymer and the unmodified polymer. Specifically, there can bementioned a method in which a GPC is performed using a column packedwith a polar substance (such as silica), which adsorbs only the modifiedpolymers, together with an internal standard substance which is notadsorbed on such a column; and a method in which GPC of a polymer isperformed prior to and after modification, and the amount of themodified polymer fraction is calculated, based on the change in thechromatogram and molecular weight of the polymer, the change occurringbetween the measurement prior to and the measurement after modification.

Examples of first-order modifiers used for producing the first-ordermodified, hydrogenated polymer of the present invention or a precursoryfirst-order modified polymer include the modifiers described in ExaminedJapanese Patent Application Publication No. Hei 4-39495 (correspondingto U.S. Pat. No. 5,115,035). Especially preferred first-order modifiersare as follows:

-   -   tetraglycidyl-m-xylenediamine,        tetraglycidyl-1,3-bisaminomethylcyclohexane,        tetraglycidyl-p-phenylene-diamine,        tetraglycidyldiaminodiphenylmethane, di-glycidylaniline,        diglycidyl-o-toluidine, γ-glycidoxyethyltrimethoxysilane,        γ-glycidoxypropyltrimethoxysilane,        γ-glycidoxybutyltrimethoxysilane,        γ-glycidoxypropyltriethoxysilane,        γ-glycidoxypropyltripropoxysilane and        γ-glycidoxypropyltributoxysilane;        γ-glycidoxypropyltriphenoxysilane,        γ-glycidoxypropylmethyldimethoxysilane,        γ-glycidoxypropylethyldimethoxysilane,        γ-glycidoxypropylethyldiethoxysilane,        γ-glycidoxypropylmethyldiethoxysilane,        γ-glycidoxypropylmethyldipropoxysilane,        γ-glycidoxypropylmethyldibutoxysilane,        γ-glycidoxypropylmethyldiphenoxysilane,        γ-glycidoxypropyldimethylmethoxysilane,        γ-glycidoxypropyldiethylethoxysilane and        γ-glycidoxypropyldimethylethoxysilane;    -   γ-glycidoxypropyldimethylphenoxysilane,        γ-glycidoxypropyldiethylmethoxysilane,        γ-glycidoxypropylmethyldiisopropenoxysilane,        bis(γ-glycidoxypropyl)dimethoxysilane,        bis(γ-glycidoxypropyl)diethoxysilane,        bis(γ-glycidoxypropyl)dipropoxysilane,        bis(γ-glycidoxypropyl)dibutoxysilane,        bis(γ-glycidoxypropyl)diphenoxysilane,        bis(γ-glycidoxypropyl)methylmethoxysilane and        bis(γ-glycidoxypropyl)methylethoxysilane;        bis(γ-glycidoxypropyl)methylpropoxysilane,        bis(γ-glycidoxypropyl)methylbutoxysilane,        bis(γ-glycidoxypropyl)methylphenoxysilane,        tris(γ-glycidoxypropyl)methoxysilane,        γ-methacryloxypropyltrimethoxysilane,        γ-methacryloxypropyltriethoxysilane,        γ-methacryloxymethyltrimethoxysilane,        γ-methacryloxyethyltriethoxysilane,        bis(γ-methacryloxypropyl)dimethoxysilane,        tris(γ-methacryloxypropyl)methoxysilane,        β-(3,4-epoxycyclohexyl)ethyl-trimethoxysilane and        β-(3,4-epoxycyclohexyl)ethyl-triethoxysilane;    -   β-(3,4-epoxycyclohexyl)ethyl-tripropoxysilane,        β-(3,4-epoxycyclohexyl)ethyl-tributoxysilane,        β-(3,4-epoxycyclohexyl)ethyl-triphenoxysilane,        β-(3,4-epoxycyclohexyl)propyl-trimethoxysilane,        β-(3,4-epoxycyclohexyl)ethyl-methyldimethoxysilane,        β-(3,4-epoxycyclohexyl)ethyl-ethyldimethoxysilane,        β-(3,4-epoxycyclohexyl)ethyl-ethyldiethoxysilane,        β-(3,4-epoxycyclohexyl)ethyl-methyldiethoxysilane,        β-(3,4-epoxycyclohexyl)ethyl-methyldipropoxysilane and        β-(3,4-epoxycyclohexyl)ethyl-methyldibutoxysilane; and    -   β-(3,4-epoxycyclohexyl)ethyl-methyldiphenoxysilane,        β-(3,4-epoxycyclohexyl)ethyl-dimethylmethoxysilane,        β-(3,4-epoxycyclohexyl)ethyl-diethylethoxysilane,        β-(3,4-epoxycyclohexyl)ethyl-dimethylethoxysilane,        β-(3,4-epoxycyclohexyl)ethyl-dimethylpropoxysilane,        β-(3,4-epoxycyclohexyl)ethyl-dimethylbutoxysilane,        β-(3,4-epoxycyclohexyl)ethyl-dimethylphenoxysilane,        β-(3,4-epoxycyclohexyl)ethyl-diethylmethoxysilane, and        β-(3,4-epoxycyclohexyl)ethyl-methyldiisopropeneoxysilane.

Further, use can be made of the following first-order modifiers:N-substituted amino ketones, such as 4-dimethylaminobenzophenone,4-diethylaminobenzophenone, 4-di-t-butylaminobenzophenone,4-diphenylaminobenzophenone, 4,4′-bis(dimethylamino)benzophenone,4,4′-bis(diethylamino)benzophenone,4,4′-bis(di-t-butyl-amino)benzophenone,4,4′-bis(diphenylamino)benzophenone, 4,4′-bis(divinylamino)benzophenone,4-dimethylaminoacetophenone, 4-diethylaminoacetophenone,1,3-bis(di-phenylamino)-2-propanone and1,7-bis(methylethylamino)-4-heptanone;

-   -   N-substituted aminoaldehydes, such as 4-diethylaminobenzaldehyde        and 4-divinylaminobenzaldehyde; N-substituted lactams, such as        N-methyl-β-propiolactam, N-t-butyl-β-propiolactam,        N-phenyl-β-propiolactam, N-methoxyphenyl-β-propiolactam,        N-naphthyl-β-propiolactam, N-methyl-2-pyrrolidone,        N-t-butyl-2-pyrrolidone, N-phenylpyrrolidone,        N-methoxyphenyl-2-pyrrolidone, N-vinyl-2-pyrrolidone,        N-benzyl-2-pyrrolidone, N-naphthyl-2-pyrrolidone,        N-methyl-5-methyl-2-pyrrolidone,        N-methyl-3,3′-dimethyl-2-pyrrolidone,        N-t-butyl-3,3′-dimethyl-2-pyrrolidone,        N-phenyl-3,3′-dimethyl-2-pyrrolidone, N-methyl-2-piperidone,        N-t-butyl-2-piperidone, N-phenylpiperidone,        N-methoxyphenyl-2-piperidone, N-vinyl-2-piperidone,        N-benzyl-2-piperidone, N-naphthyl-2-piperidone,        N-methyl-3,3′-dimethyl-2-piperidone,        N-phenyl-3,3′-dimethyl-2-piperidone, N-methyl-ε-caprolactam,        N-phenyl-ε-caprolactam, N-methoxyphenyl-ε-caprolactam,        N-vinyl-ε-caprolactam, N-benzyl-ε-caprolactam,        N-naphthyl-ε-caprolactam, N-methyl-ω-lauryl lactam,        N-phenyl-ω-lauryl lactam, N-t-butyllauryl lactam,        N-vinyl-ω-lauryl lactam and N-benzyl-ω-lauryl lactam;        N-substituted ethyleneureas, such as        1,3-dimethyl-2-imidazolidinone, 1,3-diethyl-2-imidazolidinone,        1,3-dipropyl-2-imidazolidinone,        1-methyl-3-ethyl-2-imidazolidinone,        1-methyl-3-propyl-2-imidazolidinone,        1-methyl-3-methyl-2-imidazolidinone and        1,3-dimethyl-3,4,5,6-tetrahydropyrimidinone; polyglycidyl ethers        of a polyhydric alcohol, such as ethylene glycol diglycidyl        ether and glycerin triglycidyl ether; polyglycidyl ethers of an        aromatic compound having 2 or more phenol groups, such as        4,4′-diglycidyl bisphenol A; polyepoxy compounds, such as        1,4-diglycidylbenzene, 1,3,5-triglycidylbenzene and polyepoxized        liquid polybutadiene; and diglicidylamino compounds, such as        tetraglycidyl m-xylenediamine, tetraglycidyl        1,3-bis(aminomethylcyclohexane), tetraglycidyl        p-phenylenediamine, diglycidylaniline, diglycidyl        aminomethylcyclohexane and diglycidyl o-toluidine.

Preferred example of a first-order modifier is a multifunctionalcompound having 2 or more epoxy groups and 1 or more nitrogen-containinggroup in the molecule thereof. More preferred example of a first-ordermodifier is a compound represented by the following formula:

-   -   wherein each of R¹ and R² independently represents a C₁-C₁₀        hydrocarbon group, a C₁-C₁₀ ether or a C₁-C₁₀ hydrocarbon group        containing a tertiary amine,    -   each of R³ and R⁴ independently represents a hydrogen atom, a        C₁-C₂₀ hydrocarbon group, a C₁-C₂₀ ether or a C₁-C₂₀ hydrocarbon        group containing a tertiary amine,    -   R⁵ represents a C₁-C₁₂ hydrocarbon group, a C₁-C₁₂ ether, or a        C₁-C₁₂ hydrocarbon group containing at least one functional        group selected from the group consisting of a tertiary amine, an        epoxy group, a carbonyl group and a halogen atom, and    -   n represents an integer of 1 to 6.

With respect to the first-order modifier, it is recommended that theamount of the first-order modifier used for producing the modifiedpolymer is from more than 0.5 equivalent to not more than 10equivalents, preferably from more than 0.7 equivalent to not more than 5equivalents, more preferably from more than 1 equivalent to not morethan 4 equivalents, relative to one equivalent of the living terminal ofthe base polymer. In the present invention, the amount of the livingterminal of the base polymer can be calculated from the number averagemolecular weight of the base polymer.

The first-order modified, hydrogenated polymer of the present inventioncan be obtained by hydrogenating the thus obtained first-order modified,unhydrogenated polymer in the below-mentioned manner. Further, when theprecursory first-order modified polymer used as a precursor of thesecond-order modified polymer of the present invention is partiallyhydrogenated, the hydrogenation can be performed in the below-mentionedmanner.

With respect to the hydrogenation catalyst, there is no particularlimitation, and any of the conventional hydrogenation catalysts can beused. Examples of hydrogenation catalysts include:

-   -   (1) a carried, heterogeneous hydrogenation catalyst comprising a        carrier (such as carbon, silica, alumina or diatomaceous earth)        having carried thereon a metal, such as Ni, Pt, Pd or Ru;    -   (2) the so-called Ziegler type hydrogenation catalyst which uses        a transition metal salt (such as an organic acid salt or        acetylacetone salt of a metal, such as Ni, Co, Fe or Cr) in        combination with a reducing agent, such as an organoaluminum;        and    -   (3) a homogeneous hydrogenation catalyst, such as the so-called        oraganometal complex of an organometal compound containing a        metal, such as Ti, Ru, Rh or Zr. Specific examples of        hydrogenation catalysts include those which are described in        Examined Japanese Patent Publication Nos. Sho 42-8704 and Sho        43-6636, Examined Japanese Patent Publication No. Sho 63-4841        (corresponding to U.S. Pat. No. 4,501,857) and Examined Japanese        Patent Publication No. Hei 1-37970 (corresponding to U.S. Pat.        No. 4,673,714), and Examined Japanese Patent Publication Nos.        Hei 1-53851 and Hei 2-9041. As preferred examples of        hydrogenation catalysts, there can be mentioned a titanocene        compound and a mixture of a titanocene compound and a reductive        organometal compound.

Examples of titanocene compounds include those which are described inUnexamined Japanese Patent Application Laid-Open Specification No. Hei8-109219. As specific examples of titanocene compounds, there can bementioned compounds, each independently having at least one ligand(e.g., biscyclopentadienyltitanium di-chloride andmonopentamethylcyclopentadienyltitanium trichloride) having a(substituted) cyclopentadienyl skeleton, an indenyl skeleton or afluorenyl skeleton. Examples of reductive organometal compounds includeorganic alkali metal compounds, such as an organolithium compound; anorganomagnesium compound; an organoaluminum compound; an organoboroncompound; and an organozinc compound.

The hydrogenation reaction is generally conducted at 0 to 200° C.,preferably 30 to 150° C. The hydrogen pressure in the hydrogenationreaction is generally in the range of from 0.1 to 15 MPa, preferablyfrom 0.2 to 10 MPa, more preferably from 0.3 to 7 MPa. The hydrogenationreaction time is generally in the range of from 3 minutes to 10 hours,preferably from 10 minutes to 5 hours. The hydrogenation reaction may beperformed either in a batchwise manner or in a continuous manner.Further, the hydrogenation reaction may be performed in a manner whereina batchwise operation and a continuous operation are used incombination.

By the above-mentioned method, a solution of an unhydrogenated,first-order modified polymer in a solvent used, or a solution of afirst-order modified, hydrogenated polymer in a solvent used isobtained. If desired, before the separation of the first-order modifiedpolymer or the first-order modified, hydrogenated polymer, a catalystresidue may be separated from the solution. Examples of methods forseparating the first-order modified polymer or the first-order modified,hydrogenated polymer from the solution include a method in which a polarsolvent, such as acetone or alcohol (which is a poor solvent for thepolymer), is added to the solution containing the polymer, therebyprecipitating the polymer, followed by recovery of the polymer; a methodin which the solution containing the polymer is added to hot water,while stirring, followed by removal of the solvent by steam stripping;and a method in which the solution containing the polymer is directlyheated to evaporate the solvent.

Next, a second-order modifier having a functional group which isreactive to the functional group of the first-order modifier group (y)of the first-order modified polymer is reacted with the first-ordermodified polymer, thereby obtaining a second-order modified polymercomprising a base polymer (β) and a functional group-containing modifiergroup (δ) bonded to the base polymer (β). The second-order modifier usedfor producing the second-order modified polymer is at least one memberselected from the group consisting of a functional monomer and afunctional oligomer.

The functional monomer used in the present invention is a modifierhaving a functional group which is reactive to the functional group ofthe first-order modifier group (γ) of the first-order modified polymer.The functional monomer preferably has at least one functional groupselected from the group consisting of an amino group, a carboxyl group,an acid anhydride group, an isocyanate group, an epoxy group, a silanolgroup and an alkoxysilane group, more preferably at least one functionalgroup selected from the group consisting of a carboxyl group, an acidanhydride group, an isocyanate group, an epoxy group, a silanol groupand an alkoxysilane group.

Specific examples of functional monomers are as follows. Examples offunctional monomers having a carboxyl group include aliphatic carboxylicacids, such as maleic acid, oxalic acid, succinic acid, adipic acid,azelaic acid, sebacic acid, dodecanedicarboxylic acid, carbalic acid,cyclohexanedicarboxylic acid and cyclopentanedicarboxylic acid; andaromatic carboxylic acids, such as terephthalic acid, isophthalic acid,o-phthalic acid, naphthalenedicarboxylic acid, biphenyldicarboxylicacid, trimesic acid, trimellitic acid and pyromellitic acid. Examples offunctional monomers having an acid anhydride group include maleicanhydride, itaconic anhydride, pyromellitic anhydride,cis-4-cyclohexane-1,2-dicarboxylic acid anhydride,1,2,4,5-benzenetetracarboxylic acid dianhydride and5-(2,5-dioxytetrahydroxyfuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylicacid anhydride. Examples of functional monomers having an isocyanategroup include toluylene diisocyanate, diphenylmethane diisocyanate andmulti-functional aromatic isocyanates. Examples of functional monomershaving an alkoxysilane group includebis-(3-triethoxysilylpropyl)-tetrasulfane and ethoxysiloxane oligomers.Examples of functional monomers having an epoxy group includetetraglycidyl-1,3-bis-aminomethyl-cyclohexane,tetraglycidyl-m-xylenediamine, diglycidylaniline, ethylene glycoldiglycidyl, propylene glycol diglycidyl and terephthalic acid diglycidylester acrylate.

In the present invention, especially preferred examples of functionalmonomers include a carboxylic acid having 2 or more carboxyl groups oran anhydride thereof; and crosslinking agents having 2 or more of agroup selected from the group consisting of an acid anhydride group, anisocyanate group, an epoxy group, a silanol group or an alkoxysilanegroup. Specific examples of the especially preferred crossliking agentsinclude maleic anhydride, pyromellitic anhydride, toluylene diisocyanateand tetraglycidyl-1,3-bisaminomethylcyclohexane.

With respect to the functional oligomers used in the present invention,there is no particular limitation as long as the oligomers have afunctional group which is reactive to the functional group (including aterminal functional group) of the first-order modifier group (y) of thefirst-order modified polymer. Preferred examples of functional oligomersinclude oligomers having at least one functional group selected from thegroup consisting of an amino group, a carboxyl group, an acid anhydridegroup, an isocyanate group, an epoxy group, a silanol group and analkoxysilane group.

The number average molecular weight of a functional oligomer isgenerally from 300 to 30,000, preferably from 500 to 15,000, morepreferably from 1,000 to 20,000. The functional oligomer can be producedby a conventional method, for example by anionic polymerization,cationic polymerization, radical polymerization, condensationpolymerization and addition polymerization.

Specific examples of functional oligomers include oligomers having atleast one functional group mentioned above, such as a polybutadieneoligomer and a hydrogenation product thereof, a polyisoprene oligomerand a hydrogenation product thereof, a polyethylene oligomer, apolypropylene oligomer, a polyethylene oxide oligomer, a polypropyleneoxide oligomer, an oligomeric ethylene oxide/propylene oxide copolymer,a saponification product of an oligomeric ethylene/vinyl acetatecopolymer, silicone oil and an oligomeric copolymer obtained bycopolymerizing a functional vinyl monomer having at least one of theabove-mentioned functional group and another vinyl monomercopolymerizable therewith.

Specific examples of functional vinyl monomer having at least one of theabove-mentioned functional group include glycidylacrylate,glycidylmethacrylate, β-methylglycidylacrylate,β-methylglycidylmethacrylate, allylglycidylether, monoglycidyl ester ofmaleic acid, monoglycidyl ester of itaconic acid and 3,4-epoxybutene.Further examples of functional vinyl monomer include3,4-epoxy-3-methyl-1-butene, 3,4-epoxy-1-pentene,3,4-epoxy-3-methylpentene, 5,6-epoxy-1-hexene, vinylcyclohexenemonoxide, styrene P-glycidyl ether, hydroxystyrene, 2-hydroxyethylmethacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl methacrylate,polyethylene glycol monomethacrylate, allylalcohol, maleic anhydride anditaconic anhydride.

Specific examples of vinyl monomers which are copolymerizable with theabove-mentioned functional vinyl monomer include ethylene, C₃-C₁₂α-olefins, such as propylene, 1-butene, isobutylene, 4-methyl-1-pentene,1-octene, styrene, o-methylstyrene, p-methylstyrene,p-tert-butylstyrene, 1,3-dimethylstyrene, α-methylstyrene,vinylnaphthalene, vinylanthracene, vinyl acetate, vinyl chloride andacrylonitrile. Further examples of vinyl monomers includemethacrylonitrile, methyl methacrylate, ethyl methacrylate, propylmethacrylate, isopropyl methacrylate, butyl methacrylate, isobutylmethacrylate, tert-butyl methacrylate, octyl methacrylate, 2-ethylhexylmethacrylate, methyl acrylate, ethyl acrylate, propyl acrylate,isopropyl acrylate, butyl acrylate, isobutyl acrylate, tert-butylacrylate, octyl acrylate and 2-ethylhexyl acrylate. These vinyl monomerscan be used individually or in combination.

Further, in the present invention, polyamide oligomers, polyesteroligomers and polyurethane oligomers having a molecular weight in theabove-mentioned range can be used as a functional oligomer.

The amount of the second-order modifier used for producing thesecond-order modified polymer of the present invention is from 0.3 to 10moles, preferably from 0.4 to 5 moles, more preferably from 0.5 to 4moles, relative to one equivalent of the functional group of thefirst-order modifier group (γ) of the first-order modified polymer.

There is no particular limitation with respect to the structure of thesecond-order modified polymer of the present invention, but thesecond-order modified polymer is preferably represented by a formulaselected from the group consisting of the following formulae (VI) to(X):

-   -   wherein:    -   A² represents a unit which is represented by any one of the        following formulae (a-2) and (b-2):    -   B² represents a unit which is represented by any one of the        following formulae (c-2) to (e-2):    -   C² represents a unit which is represented by any one of the        following formulae (f-2) to (h-2):    -   D² represents a unit which is represented by the following        formula (i-2):        —R⁸—NR³—X¹   (i-2)    -   E² represents a unit which is represented by the following        formula (j-2):        —R⁹—P¹, and   (j-2)    -   F² represents a unit which is represented by any one of the        following formulae (k-2) to (m-2):    -   wherein:    -   X¹ represents a unit which is represented by any one of the        following formulae (n-2) to (s-2):    -   wherein, in the formulae (VI) to (VIII) and (a-2) to (s-2):        -   N represents a nitrogen atom, Si represents a silicon atom,            O represents an oxygen atom, C represents a carbon atom, and            H represents a hydrogen atom,        -   p¹ represents the base polymer,        -   R^(1a) represents a trivalent aliphatic C₁-C₄₈ hydrocarbon            group,        -   each of R^(1b), R⁴, R⁸ to R¹⁰ and R¹³ to R²⁰ independently            represents a C₁-C₄₈ alkylene group,        -   each of R², R³ and R¹¹ independently represents a C₁-C₄₈            alkyl group, a C₆-C₄₈ aryl group, an alkylaryl group            comprised of C₁-C₄₈ alkyl and C₆-C₄₈ aryl, an aralkyl group            comprised of C₁-C₄₈ alkyl and C₆-C₄₈ aryl, or a C₃-C₄₈            cycloalkyl group,        -   wherein each of R^(1a), R^(1b), R³, R⁴, R⁸ to R¹⁰, R¹³ to            R¹⁵ and R¹⁷ to R²⁰ optionally, independently has at least            one functional group selected from the group consisting of a            hydroxyl group, an epoxy group, an amino group, a silanol            group and a C₁-C₂₄ alkoxysilane group,        -   each of R⁵ to R⁷ and R¹² independently represents a hydrogen            atom, a C₁-C₄₈ alkyl group, a C₆-C₄₈ aryl group, an            alkylaryl group comprised of C₁-C₄₈ alkyl and C₆-C₄₈ aryl,            an aralkyl group comprised of C₁-C₄₈ alkyl and C₆-C₄₈ aryl,            or a C₃-C₄₈ cycloalkyl group,        -   wherein each of R^(1a), R^(1b), R² to R⁴ and R⁸ to R²⁰            optionally, independently has bonded thereto at least one            atom selected from the group consisting of an oxygen atom, a            nitrogen atom, a sulfur atom, and a silicon atom, the at            least one atom being present in a linkage other than a            hydroxyl group, an epoxy group, an amino group, a silanol            group and an alkoxysilane group, and        -   each of t, u, v and x is independently an integer of 0 or            more, provided that both t and u are not simultaneously 0,            and each of w, y, z and α is independently an integer of 1            or more.

Further, the present invention provides a method for producing thesecond-order modified polymer by the use of the above-mentionedsecond-order modifier. Specifically, the present invention provides amethod comprising the following steps (1) and (2):

-   -   (1) providing a first-order modified polymer comprising:        -   (β) a base polymer which is unhydrogenated or at least            partially hydrogenated and which is at least one member            selected from the group consisting of the above-mentioned            polymers (β-1) to (β-3), and        -   (γ) a functional group-containing first-order modifier group            bonded to the base polymer (β),            -   wherein the first-order modified polymer is produced by                a process in which a base polymer having a living                terminal is produced by a living anionic polymerization                using an organolithium compound as a polymerization                catalyst, and a functional group-containing first-order                modifier is addition-bonded to the living terminal of                the base polymer to obtain a first-order modified                polymer, optionally followed by partial or complete                hydrogenation of the obtained first-order modified                polymer, and    -   (2) reacting a second-order modifier with the first-order        modified polymer to thereby form (δ) a functional        group-containing modifier group, wherein the second-order        modifier has a functional group which is reactive to the        functional group of the first-order modifier group (γ) of the        first-order modified polymer, and wherein the second-order        modifier is used in an amount of 0.3 to 10 moles, relative to        one equivalent of the functional group of the first-order        modifier group (γ) of the first-order modified polymer,    -   thereby obtaining a second-order modified polymer,        -   wherein the functional group-containing first-order modifier            group (γ) of the first-order modified polymer comprises at            least one functional group represented by a formula selected            from the group consisting of the above-mentioned            formulae (a) to (m).

The second-order modified polymer of the present invention can beproduced by conventional methods. Examples of conventional methodsinclude a method using solution reaction (described below), a methodusing melt-kneading (described below) and a method (described below) inwhich the components are reacted with each other in a state in whichthey are dissolved or dispersed together in a solvent. Specifically, thesecond-order modified polymer can be produced by the following methods(1) to (4):

-   -   (1) The first-order modified polymer is produced by a process in        which a base polymer having a living terminal is produced by a        living anionic polymerization, and a functional group-containing        first-order modifier is addition-bonded to the living terminal        of the base polymer to obtain a first-order modified polymer,        optionally followed by partial or complete hydrogenation of the        obtained first-order modified polymer. Then, a second-order        modifier (functional monomer and/or a functional oligomer)        having a functional group which is reactive to the functional        group of the first-order modifier group of the first-order        modified polymer is reacted with the first-order modified        polymer. The temperature at which the first-order modified        polymer and the second-order modifier are reacted with each        other is generally −10 to 150° C., preferably 30 to 120° C. The        reaction time for this method varies depending on other        conditions, but it is generally within 3 hours, preferably from        several seconds to 1 hour.    -   (2) The first-order modified polymer is produced by a process in        which a base polymer having a living terminal is produced by a        living anionic polymerization, and a functional group-containing        first-order modifier is addition-bonded to the living terminal        of the base polymer to obtain a first-order modified polymer,        optionally followed by partial or complete hydrogenation of the        obtained first-order modified polymer. The obtained first-order        modified polymer is treated with an active hydrogen-containing        compound. Examples of active hydrogen-containing compounds        include water; alcohols, such as methanol and ethanol; and        inorganic acids, such as hydrochloric acid, sulfuric acid,        phosphoric acid and carbonic acid. Then, a second-order modifier        having a functional group which is reactive to the functional        group of the first-order modifier group of the first-order        modified polymer is reacted with the resultant first-order        modified polymer. The reaction conditions for reacting the        first-order modified polymer with the second-order modifier are        the same as those for method (1) above.    -   (3) A first-order modified polymer or a hydrogenation product        thereof is dissolved or dispersed in a solvent and, then, the        first-order modified polymer and a second-order modifier having        a functional group which is reactive to the functional group of        the first-order modifier group of the first-order modified        polymer are reacted with each other in a state in which they are        dissolved or dispersed together in the solvent. There is no        particular limitation with respect to the solvent as long as it        is capable of dissolving or dispersing each of the components.        Examples of solvents include hydrocarbon solvents, such as an        aliphatic hydrocarbon, an alicyclic hydrocarbon and an aromatic        hydrocarbon; halogen-containing solvents; ester solvents; and        ether solvents. The reaction conditions for reacting the        first-order modified polymer and the second-order modifier are        the same as those for method (1) above.    -   (4) A first-order modified polymer or a hydrogenation product        thereof is melt-kneaded with a second-order modifier having a        functional group which is reactive to the functional group of        the first-order modifier group of the first-order modified        polymer to thereby effect a reaction between the first-order        modified polymer and the second-order modifier. For example, the        melt-kneading can be performed using a conventional mixing        machine, such as a Banbury mixer, a single-screw extruder, a        twin-screw extruder, a co-kneader or a multi-screw extruder. The        melt-kneading temperature is generally in the range of from 50        to 250° C., preferably from 80 to 230° C., and the melt-kneading        time is generally less than 3 hours, preferably from several        seconds to 1 hour.

In each of the above-mentioned methods (1) to (3), the second-ordermodified polymer is obtained in the form of a solution. If desired, fromthe obtained solution, the catalyst residue may be removed and thepolymer may be separated. Examples of methods for separating the polymerfrom the solution include a method in which a polar solvent (which is apoor solvent for the polymer), such as acetone or alcohol, is added tothe solution containing the polymer, thereby precipitating the polymer,followed by recovery of the polymer; a method in which the solutioncontaining the polymer is added to hot water, while stirring, followedby removal of the solvent by steam stripping; and a method in which thesolution containing the polymer is directly heated to evaporate thesolvent.

In the present invention, the first-order modified, hydrogenated polymerand the second-order modified polymer may contain, added thereto, any ofthe conventional stabilizers, such as phenol type stabilizers,phosphorus type stabilizers, sulfur type stabilizers and amine typestabilizers. There is no particular limitation with respect to thestabilizer used in the present invention, and conventional stabilizerscan be used. Examples of conventional stabilizers include variousantioxidants used in this technical field, such as phenol typestabilizers (e.g., 2,6-di-tert-butyl-4-methylphenol andn-octadecyl-3-(3′,5′-di-tert-butyl-4′-hydroxyphenyl)propionate); organicphosphite compounds (e.g., tris-(2,4-di-tert-butylphenyl)phosphite); andsulfur-containing phenol type stabilizers (e.g.,4,6-bis[(octylthio)methyl]-o-cresol). These antioxidants can be usedindividually or in combination.

Each of the first-order modified, hydrogenated polymer and thesecond-order modified polymer of the present invention, as such or incombination with various additives, can be formed into a practicallyuseful shaped article by using a conventional molding method. Examplesof conventional molding methods include extrusion molding method,injection molding method, two-color injection molding method, sandwichmolding method, hollow molding method, compression molding method,vacuum molding method, rotational molding method, powder slush moldingmethod, foam molding method, laminate molding method, calender moldingmethod and blow molding method. If desired, the thus obtained shapedarticle may be subjected to processing, such as foaming, pulverization,stretching, adhesion, printing, painting and plating. By employing suchmolding methods, the first-order modified, hydrogenated polymer, thesecond-order modified polymer and the polymer composition of the presentinvention can be individually formed into various shaped articles, suchas a sheet, a film, injection molded articles having variousmorphologies, a blow molded article, an article made by air-pressureforming, a vacuum molded article, an extrusion molded article, afoam-molded article, a nonwoven fabric, a fibrous shaped article and asynthetic leather. The obtained shaped articles can be advantageouslyused in various fields, such as the fields of a raw material for foodpackaging; a material for medical equipment; a material for householdelectrical appliances and parts thereof, electric devices and partsthereof, automobile parts, industrial parts, household goods, toys,footwears and adhesives; and an asphalt modifier.

Specific examples of automobile parts include a side mall, a grommet, aknob, a weatherstrip, a window frame and a sealant therefor, an armrest,a door grip, a steering wheel grip, a console box, a headrest, aninstrument panel, a bumper, a spoiler, and a storage cover for anair-bag device. Specific examples of medical instruments include a bloodbag, a bag for storing platelets, a transfusion (drug solution) bag, abag for artificial dialysis, a medical tubing, and a catheter. Further,the first-order modified, hydrogenated polymer, the second-ordermodified polymer or the polymer composition of the present invention canbe used in a substrate for an adhesive tape, sheet or film; a substratefor a surface protection film, an adhesive for a surface protectionfilm; an adhesive for a carpet; a stretch wrapping film; a heatshrinkable film; a coating material for a coated steel pipe; and asealant.

In still another aspect of the present invention, there is provided acomposition comprising component (A) selected from the group consistingof the first-order modified, hydrogenated polymer (A-1) of the presentinvention, the second-order modified polymer (A-2) of the presentinvention, and a first-order modified polymer (A-3) which is a precursorof the above-mentioned second-order modified polymer. Specifically, thepresent invention provides the following compositions <1> to <7>:

-   <1> A filler-containing modified polymer composition comprising    component (A) and a reinforcing filler (B).-   <2> A crosslinked, filler-containing modified polymer composition    obtained by subjecting the above-mentioned filler-containing    modified polymer composition to a crosslinking reaction in the    presence of a vulcanizing agent.-   <3> A modified polymer composition comprising component (A) and at    least one polymer (D) selected from the group consisting of a    thermoplastic resin other than component (A) and a rubbery polymer    other than component (A).-   <4> A crosslinked, modified polymer composition obtained by    subjecting the above-mentioned modified polymer composition to    melt-kneading in the presence of a vulcanizing agent.-   <5> An adhesive composition comprising component (A) and a tackifier    (E).-   <6> An asphalt composition comprising component (A) and an asphalt    (F).-   <7> A styrene resin composition obtained by subjecting a raw    material mixture to radical polymerization, the raw material mixture    comprising component (A) and component (G) which is vinyl aromatic    hydrocarbon monomer or a mixture of a vinyl aromatic hydrocarbon    monomer and a comonomer copolymerizable with the vinyl aromatic    hydrocarbon monomer.

It should be noted that the first-order modified polymer (A-3)comprises:

-   -   (β) a base polymer which is unhydrogenated or at least partially        hydrogenated and which is at least one member selected from the        group consisting of the following polymers (β-1) to (β-3):        -   (β-1) a conjugated diene polymer comprising conjugated diene            monomer units,        -   (β-2) a copolymer comprising conjugated diene monomer units            and vinyl aromatic hydrocarbon monomer units, the copolymer            having no or at least one polymer block (H) of the vinyl            aromatic hydrocarbon monomer units, wherein the copolymer            has a vinyl aromatic hydrocarbon block ratio of from 0 to            less than 50% by weight, the vinyl aromatic hydrocarbon            block ratio being defined as the percent by weight of the            vinyl aromatic hydrocarbon monomer units contained in the at            least one polymer block (H) of the vinyl aromatic            hydrocarbon monomer units, based on the total weight of            vinyl aromatic hydrocarbon monomer units contained in the            copolymer as in the unhydrogenated state, and        -   (β-3) a vinyl aromatic hydrocarbon polymer comprising vinyl            aromatic hydrocarbon monomer units, and    -   (γ) a functional group-containing first-order modifier group        bonded to the base polymer (β), wherein the functional        group-containing first-order modifier group (y) of the        first-order modified polymer (A-3) comprises at least one        functional group represented by a formula selected from the        group consisting of the above-mentioned formulae (a) to (m).

Hereinbelow, the compositions of the present invention are explained indetail.

<1> Filler-Containing Modified Polymer Composition

The present invention provides a filler-containing modified polymercomposition comprising:

-   -   100 parts by weight of component (A) selected from the group        consisting of the first-order modified, hydrogenated polymer        (A-1) of the present invention, the second-order modified        polymer (A-2) of the present invention, and a first-order        modified polymer (A-3) which is a precursor of the        above-mentioned second-order modified polymer, and    -   0.5 to 300 parts by weight of (B) a reinforcing filler. The        filler-containing modified polymer composition of the present        invention exhibits not only excellent properties with respect to        impact resilience and low heat build-up, but also improved        processability.

With respect to the reinforcing filler (B) used for producing thefiller-containing modified polymer composition of the present invention,use can be made of conventional reinforcing fillers, such as a lightcalcium carbonate, a heavy calcium carbonate, various surface treatedcalcium carbonates, magnesium carbonate, barium sulfate, magnesiumsulfate, calcium sulfate, a silica type inorganic filler, a metal oxide,a metal hydroxide and carbon. Of these, a silica type inorganic filler,a metal oxide, a metal hydroxide and carbon are preferred. Thesereinforcing fillers can be used individually or in combination.

The silica type inorganic filler used as the reinforcing filler is asolid particle composed mainly of SiO₂ or Si₃Al. Examples of silica typeinorganic fillers include silica, clay, talc, mica, diatomaceous earth,wollastonite, montmorillonite, zeolite and a fibrous inorganicsubstance, such as a glass fiber. Further, a silica type inorganicfiller having its surface rendered hydrophobic and a mixture of thesilica type inorganic filler and a non-silica type inorganic filler mayalso be used as the reinforcing filler. Among the above-exemplifiedsilica type inorganic fillers, preferred are silica and a glass fiber.Specific examples of silica include a white carbon produced by the dryprocess, a white carbon produced by the wet process, a syntheticsilicate type white carbon and the so-called colloidal silica. Thepreferred average particle diameter of the silica type inorganic filleris generally in the range of from 0.01 to 150 μm. For achieving theeffects of addition of the silica type inorganic filler, it is preferredto disperse the filler finely in the composition such that the averageparticle diameter of the silica type inorganic filler dispersed in thecomposition is in the range of from 0.05 to 1 μm, preferably from 0.05to 0.5 μm.

The metal oxide used as the reinforcing filler is a solid particlecomposed mainly of M_(x)O_(y) (wherein M represents a metal atom, andeach of x and y independently represents an integer of from 1 to 6).Examples of metal oxides include alumina, titanium oxide, magnesiumoxide and zinc oxide. Further, the metal oxide may be used in the formof a mixture thereof with an inorganic filler other than the metaloxide. The metal hydroxides used as the reinforcing filler are hydratedtype inorganic fillers, such as aluminum hydroxide, magnesium hydroxide,zirconium hydroxide, hydrated aluminum silicate, hydrated magnesiumsilicate, basic magnesium carbonate, hydrotalcite, calcium hydroxide,barium hydroxide, hydrated tin oxide and hydrated inorganic metalcompounds, such as borax. Of these, preferred are magnesium hydroxideand aluminum hydroxide.

Further, as the reinforcing filler, carbons (carbon blacks) of variousgrades, such as FT, SRF, FEF, HAF, ISAF and SAF, can be used. It ispreferred that the carbon black used has a specific surface area(measured by the nitrogen adsorption method) of 50 mg/g or more, and aDBT (dibutyl phthalate) oil absorption of 80 ml/100 g or more.

In the filler-containing modified polymer composition of the presentinvention, the amount of the reinforcing filler (B) is in the range offrom 0.5 to 300 parts by weight, preferably from 5 to 200 parts byweight, more preferably from 20 to 100 parts by weight, relative to 100parts by weight of component (A) which is the modified polymer. When theamount of the reinforcing filler (B) contained in a polymer compositionis less than 0.5 part by weight, the effect of adding the reinforcingfiller becomes unsatisfactory. On the other hand, when the amount of thereinforcing filler (B) contained in a polymer composition is more than300 parts by weight, the dispersibility of the reinforcing fillerbecomes lowered and the processability and the mechanical strength ofsuch a polymer composition becomes poor.

Preferably, the filler-containing modified polymer composition of thepresent invention further comprises 0.01 to 20 parts by weight of (C) amodifier having a functional group which is reactive to the functionalgroup of the modifier group of component (A), wherein the modifier (C)is at least one member selected from the group consisting of afunctional monomer and a functional oligomer. When component (A) is thefirst-order modified, hydrogenated polymer (A-1) or the first-ordermodified polymer (A-3), a second-order modifier can be added to thecomposition so that the polymer contained in the final compositionbecomes a second-order modified polymer. When component (A) is thesecond-order modified polymer (A-2), a third-order modifier can be addedto the composition so as to further modify the second-order modifiedpolymer contained in the final composition. The above-mentionedfunctional monomers and functional oligomers can be used as thesecond-order modifier or the third-order modifier.

The filler-containing modified polymer composition may further contain asilane coupling agent. The silane coupling agent is used to strengthenthe interaction between the modified polymer (A) and the reinforcingfiller (B), and is a compound having a group which exhibits an affinityor bonding ability to either or both of the modified polymer (A) and thereinforcing filler (B). Specific examples of silane coupling agentsinclude bis[3-(triethoxysilyl)propyl]tetrasulfide,bis[3-(triethoxysilyl)propyl]disulfide,bis-[2-(triethoxysilyl)ethyl]tetrasulfide,3-mercaptopropyl-trimethoxysilane,3-mercaptopropyl-methyldimethoxysilane,3-triethoxysilylpropyl-N,N-dimethylthiocarbamoyltetrasulfide,3-triethoxysilylpropylbenzothiazoletetrasulfide, vinyltrimethoxysilane,vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)-ethyltrimethoxysilane,3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane,p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane,3-methacryloxypropyltrimethoxysilane,3-methacryloxypropylmethyldiethoxysilane,3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane,N-2(aminoethyl)3-aminopropylmethyldimethoxysilane,N-2(aminoethyl)3-aminopropyltrimethoxysilane,N-2(aminoethyl)3-aminopropyltriethoxysilane,3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane,3-triethoxysilyl-N-(1,3-dimethylbutylidene)propylamine,N-phenyl-3-aminopropyltrimethoxysilane and3-iso-cyanatepropyltriethoxysilane. As a preferred example of the silanecoupling agent, there can be mentioned a compound having a polysulfidelinkage containing a silanol group or an alkoxysilane in combinationwith two or more sulfur atoms, wherein any of the sulfur atoms may bepresent in the form of a mercapto group. Specific examples of suchpreferred silane coupling agents includebis[3-(triethoxysilyl)propyl]tetrasulfide,bis[3-(triethoxysilyl)propyl]disulfide,bis[2-(triethoxysilyl)ethyl]tetrasulfide,3-mercaptopropyl-trimethoxysilane,3-mercaptopropyl-methldimethoxysilane,3-triethoxysilylpropyl-N,N-dimethylthiocarbamoyltetrasulfide and3-triethoxysilylpropylbenzothiazoletetrasulfide. The amount of thesilane coupling agent is generally in the range of from 0.1 to 30% byweight, preferably from 0.5 to 20% by weight, more preferably from 1 to15% by weight, based on the weight of the reinforcing filler (B).

In the present invention, for improving the processability of thefiller-containing modified polymer composition, a rubber-softening agentmay be added. As the rubber-softening agent, it is suitable to use amineral oil, or a liquid or low molecular weight synthetic softeningagent. It is especially preferred to use a mineral oil type softeningagent, such as a process oil or extender oil, which is generally usedfor softening a rubber, for increasing the volume of a rubber or forimproving the processability of a rubber. The mineral oil type softeningagent is a mixture of an aromatic compound, a naphthene and a chainparaffin. With respect to the mineral oil type softening agents, asoftening agent in which the number of carbon atoms constituting theparaffin chains is 50% or more (based on the total number of carbonatoms present in the softening agent) is generally referred to as a“paraffin type softening agent”; a softening agent in which the numberof carbon atoms constituting the naphthene rings is 30 to 45% (based onthe total number of carbon atoms present in the softening agent) isgenerally referred to as a “naphthene type softening agent”; and asoftening agent in which the number of carbon atoms constituting thearomatic rings is more than 30% (based on the total number of carbonatoms present in the softening agent) is generally referred to as an“aromatic type softening agent”. In the present invention, a naphthenetype softening agent and/or paraffin type softening agent is preferred.The reinforcing filler-containing composition may also contain asynthetic softening agent, such as a polybutene and a low molecularweight polybutadiene. However, the above-mentioned mineral oil typesoftening agent is more preferred, in view of the effect of using thesoftening agent in the composition. The amount of the rubber-softeningagent used in the reinforcing filler-containing composition is generallyin the range of from 10 to 100 parts by weight, preferably from 10 to 90parts by weight, more preferably from 30 to 90 parts by weight, relativeto 100 parts by weight of component (A). When the amount of therubber-softening agent exceeds 100 parts by weight, the rubber-softeningagent is likely to bleed out from the composition, thereby leading to adanger that the surface tack of the composition occurs.

In the present invention, a modified polymer can be used in combinationwith a rubbery polymer other than the modified polymer (A). As thespecific examples of the rubbery polymer, use can be made of the rubberpolymers mentioned as component (D) in connection with item <3> below.When a rubbery polymer is used in combination with the modified polymer,the rubbery polymer is generally used in an amount of from 5 to 400parts by weight, preferably 5 to 200 parts by weight, more preferably 10to 100 parts by weight, relative to 100 parts by weight of the modifiedpolymer (A).

In the present invention, if desired, an additive may be added to thefiller-containing modified polymer composition comprising component (A)and a reinforcing filler (B) so long as the properties of thefiller-containing modified polymer composition are not harmfullyaffected. For example, in the present invention, the additives asdescribed in “Gomu Purasuchikku Haigou Yakuhin (Additives for Rubber andPlastic)” (Rubber Digest Co., Ltd., Japan) can be used. Examples ofadditives include a softening agent, a thermal stabilizer, an antistaticagent, a weathering stabilizer, an antioxidant, a filler, a coloringagent and a lubricant. Examples of softening agents that may be used forcontrolling the hardness and fluidity of the final product include aliquid paraffin, a castor oil and a linseed oil. The softening agent maybe added just before or during the kneading of the components for thefiller-containing modified polymer composition, or may be incorporatedinto the modified polymer used as component (A) during the productionthereof.

With respect to the method for mixing the modified polymer (A) and thereinforcing filler (B), and optionally other components, there is noparticular limitation, and any of the conventional methods can beemployed. For example, the filler-containing modified polymercomposition of the present invention can be produced by melt-kneadingmethod using a conventional mixing machine, such as an open roll, aBanbury mixer, a kneader, a single-screw extruder, a twin-screwextruder, a multi-screw extruder, or a method in which the componentsfor the composition are added to a solvent, to thereby obtain a solutionor dispersion of a mixture of the components in the solvent, followed byheating to remove the solvent. From the viewpoint of productivity of thecomposition and uniform mixing of the components of the composition, itis preferred to use the melt-kneading method using a roll, a Banburymixer, a kneader or an extruder. When preparing the filler-containingmodified polymer composition, the components contained in thecomposition can be mixed either all at once or in parts.

<2> Crosslinked, Filler-Containing Modified Polymer Composition

The present invention provides a crosslinked, filler-containing modifiedpolymer composition obtained by subjecting the above-mentionedfiller-containing modified polymer composition <1> to a crosslinkingreaction in the presence of a vulcanizing agent.

Examples of vulcanizing agents include a radical generator, such as anorganic peroxide and an azo compound, an oxime compound, a nitrosocompound, a polyamine compound, sulfur and a sulfur-containing compound(such as sulfur monochloride, sulfur dichloride, a disulfide compoundand a polymeric polysulfide compound). The vulcanizing agent isgenerally used in an amount of from 0.01 to 20 parts by weight,preferably 0.1 to 15 parts by weight, relative to 100 parts by weight ofcomponent (A) (i.e., a modified polymer).

Examples of organic peroxides used as the vulcanizing agent includedicumyl peroxide, di-tert-butyl peroxide,2,5-dimethyl-2,5-di(tert-butylperoxy)hexane,2,5-dimethyl-2,5-di(tert-butylperoxy)hexyne-3,1,3-bis(tertbutylperoxyisopropyl)benzene,1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane,n-butyl-4,4-bis(tert-butylperoxy)valerate, benzoyl peroxide,p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, tert-butylperoxybenzoate, tert-butyl perbenzoate, tert-butylperoxyisopropylcarbonate, diacetyl peroxide, lauroyl peroxide and tert-butyl cumylperoxide. Among the above-mentioned organic peroxides, from theviewpoint of low odor and scorch stability, preferred are2,5-dimethyl-2,5-di(tert-butylperoxy)hexane,2,5-dimethyl-2,5-di(tert-butylperoxy)hexyne-3,1,3-bis(tert-butylperoxyisopropyl)benzene,1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane,n-butyl-4,4-bis(tert-butylperoxy)valerate and di-tert-butyl peroxide.

In the above-mentioned vulcanization reaction, a vulcanizationaccelerator may be used in a desired amount. Examples of vulcanizationaccelerators include a sulphenic amide type accelerator, a guanidinetype accelerator, a thiuram type accelerator, an aldehyde-amine typeaccelerator, an aldehyde-ammonia type accelerator, a thiazole typeaccelerator, a thiourea type accelerator and a dithiocarbamate typeaccelerator. An auxiliary vulcanizing agent, such as zinc oxide andstearic acid, may also be used in a desired amount.

Further, when the above-mentioned organic peroxide is used forcrosslinking (vulcanizing) the reinforcing filler-containingcomposition, a vulcanization accelerator can be used in combination withthe organic peroxide. Examples of vulcanization accelerators which maybe used in combination with the organic peroxide include sulfur;auxiliaries for a peroxide crosslinking agent, such as p-quinonedioxime, p,p′-dibenzoylquinone dioxime, N-methyl-N-4-dinitrosoaniline,nitrosobenzene, diphenylguanidine andtrimethylolpropane-N,N′-m-phenylene dimaleimide; divinyl benzene;triallyl cyanurate; multifunctional methacrylate monomers, such asethyleneglycol dimethacrylate, diethyleneglycol dimethacrylate,polyethyleneglycol dimethacrylate, trimethylol propane trimethacrylateand allyl methacrylate; multifunctional vinyl monomers, such as vinylbutylate and vinyl stearate. The vulcanization accelerator as mentionedabove is generally used in an amount of from 0.01 to 20 parts by weight,preferably from 0.1 to 15 parts by weight, relative to 100 parts byweight of component (A) (i.e., a modified polymer).

The above-mentioned vulcanization reaction can be performed by aconventional method. For example, with respect to the reactiontemperature, the vulcanization reaction may be conducted at 120 to 200°C., preferably 140 to 180° C.

The crosslinked, filler-containing modified polymer composition obtainedby subjecting the filler-containing modified polymer composition to acrosslinking reaction may be used for producing a material for interiorand exterior parts of automobiles, a rubber cushion, a belt, a footwear,a foam, an industrial article, a tire and the like, taking advantage ofits characteristics.

<3> Modified Polymer Composition

The present invention provides a modified polymer compositioncomprising:

-   -   1 to 99 parts by weight, relative to 100 parts by weight of the        total of components (A) and (D), of component (A) selected from        the group consisting of the first-order modified, hydrogenated        polymer (A-1) of the present invention, the second-order        modified polymer (A-2) of the present invention, and a        first-order modified polymer (A-3) which is a precursor of the        above-mentioned second-order modified polymer, and    -   99 to 1 part by weight, relative to 100 parts by weight of the        total of components (A) and (D), of (D) at least one polymer        selected from the group consisting of a thermoplastic resin        other than component (A) and a rubbery polymer other than        component (A). The modified polymer composition comprising the        modified polymer of the present invention exhibits high        compatibility with at least one component (D) selected from the        group consisting of a thermoplastic resin and a rubbery polymer,        and the resultant composition exhibits excellent mechanical        strength.

Component (D) used for producing the modified polymer composition of thepresent invention is at least one polymer selected from the groupconsisting of a thermoplastic resin other than component (A) and arubbery polymer other than component (A). It is preferred that thethermoplastic resin as component (D) is a functional group-containingthermoplastic resin having a functional group which is reactive to thefunctional group of the modifier group of component (A). Specificexamples of functional group-containing thermoplastic resins include apolyester resin; a polyamide resin; a polycarbonate resin; apolyurethane resin; a polymer containing in the main chain thereof animide linkage, such as polyimide, polyaminobismaleimide(polybismaleimide), a bismaleimide triazine resin or a polyimide resin(e.g., polyamide-imide or polyether imide); a polyoxymethylene resin,such as a homopolymer of formaldehyde or trioxane, or a copolymer offormaldehyde or trioxane and at least one member selected from the groupconsisting of an aldehyde other than formaldehyde or trioxane, a cyclicether, an epoxide, an isocyanate and a vinyl compound; a polysulfoneresin, such as polyether sulfone or polyallylsulfone; a polyphenyleneether resin, such as poly(2,6-dimethyl-1,4-phenylene) ether; apolyphenylene sulfide resin, such as polyphenylene sulfide orpoly-4,4′-diphenylene sulfide; a polyallylate resin which is acondensation polymer produced from bisphenol A and phthalic acid; and apolyketone resin. Further examples of functional group-containingthermoplastic resins include a copolymer of a vinyl aromatic hydrocarbonmonomer with at least one vinyl monomer (other than the vinyl aromatichydrocarbon monomer), such as vinyl acetate, acrylic acid and an esterthereof (e.g., methyl acrylate), acrylonitrile and methacrylonitrile; anacrylonitrile/butadiene/styrene copolymer resin (ABS); amethacrylate/butadiene/styrene copolymer resin (MBS); a copolymer ofethylene with a comonomer copolymerizable with ethylene, which has anethylene monomer unit content of 50% by weight or more (e.g., anethylene/vinyl acetate copolymer or a hydrolysis product thereof); apolyethylene resin (e.g., an ethylene/acrylic acid ionomer); a copolymerof propylene with a comonomer copolymerizable with propylene, which hasa propylene monomer unit content of 50% by weight or more, such as apolypropylene resin (e.g., a propylene/ethyl acrylate copolymer); and apolyvinyl acetate resin which is a copolymer of vinyl acetate with acomonomer copolymerizable with vinyl acetate, which has a vinyl acetatemonomer unit content of 50% by weight or more, or a hydrolysis productthereof. Still further examples of functional group-containingthermoplastic resins include a polymer of acrylic acid or an ester oramide thereof; a polymer of methacrylic acid or an ester or amidethereof; a polyacrylate resin which is a copolymer of such a(meth)acrylic monomer with a comonomer copolymerizable therewith andwhich has an acrylic monomer unit content of 50% by weight or more; apolymer of acrylonitrile and/or methacrylonitrile; a nitrile resin whichis a copolymer of (meth)acrylonitrile with a comonomer copolymerizablewith (meth)acrylonitrile and which has a (meth)acrylonitrile monomerunit content of 50% by weight or more; a polyoxybenzoyl type polymer,such as a homopolymer or copolymer obtained by polycondensation ofp-hydroxybenzoic acid, terephthalic acid, isophthalic acid,4,4′-dihydroxydiphenyl or derivatives thereof.

Especially preferred functional group-containing thermoplastic resinsusable as component (D) are a polyester resin, a polyamide resin, apolycarbonate resin and a polyurethane resin. The above-mentionedthermoplastic resins can be used individually or in combination. Whensuch a functional group-containing thermoplastic resin is used ascomponent (D), the functional group-containing thermoplastic resinreacts with the functional group of the modified polymer (A) and theresultant modified polymer composition exhibits improved compatibility.

The polyester resin used as component (D) in the present inventioncontains in the molecule thereof an ester linkage. A representativeexample of such polyester resin is a polyester which has a structureobtained by a polycondensation of a dicarboxylic acid with a glycol,specifically a structure obtained by subjecting at least one memberselected from a group consisting of a dicarboxylic acid, a lower esterthereof, an acid halide thereof and an anhydride thereof, to apolycondensation with a glycol. Examples of aromatic dicarboxylic acidsor aliphatic dicarboxylic acids used as a raw material for the polyesterresin include oxalic acid, malonic acid, succinic acid, glutaric acid,pimelic acid, suberic acid, adipic acid, sebacic acid, azelaic acid,1,9-nonanedicarboxylic acid, 1,10-decanedicarboxylic acid,1,16-hexadecanedicarboxylic acid, terephthalic acid, isophthalic acid,p,p′-dicarboxydiphenyl, p-carboxyphenoxyacetic acid and 2,6-naphthalenedicarboxylic acid. These dicarboxylic acids can be used individually orin combination. Of these, preferred are terephthalic acid andisophthalic acid.

With respect to the glycol (also called “diol”) used as the other rawmaterial for the polyester resin, there are two types of glycols, namelyaliphatic glycols and aromatic glycols, such as ethylene glycol,1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,6-hexanediol,1,4-cyclohexanediol, 1,10-decanediol, neopentyl glycol and p-xyleneglycol. These glycols (diols) can be used individually or incombination. Of these, preferred are ethylene glycol and 1,4-butanediol.

As examples of polyester resins other than those mentioned above, therecan be mentioned polylactones obtained by a ring-opening polymerizationof a lactone, such as pivalolactone, β-propiolactone, ε-caprolactone andthe like. The above-mentioned polyester resins include a polyester resinhaving a hydroxyl group or a carboxyl group at the terminal thereof anda polyester resin obtained by reacting such a polyester resin with amonofunctional alcohol or a monofunctional carboxylic acid to therebyinactivate the functional group. In the present invention, the polyesterresin used as component (D) is preferably a resin having a functionalgroup at all or part of the terminals thereof, wherein the functionalgroup is reactive to the functional group of component (A). When such afunctional group-containing polyester resin is used as component (D),the functional group-containing polyester resin reacts with thefunctional group of the modified polymer (A) and the resultant modifiedpolymer composition exhibits improved compatibility. The above-mentionedpolyester resins can be used individually or in combination.

With respect to examples of polyamide resins used as component (D) inthe present invention, there can be mentioned a polycondensate of adicarboxylic acid and a diamine, a polycondensate of anα-aminocarboxylic acid, and a ring-opening polymerization product of alactam. Specific examples of such polyamide resins include nylon-4,6,nylon-6, nylon-6,6, nylon-6,10, nylon-11, nylon-12 and copolymersthereof (e.g., a nylon-6/nylon-6,6 copolymer and a nylon-6/nylon-12copolymer). It is preferred that these polyamide resins have a meltingtemperature in the range of from 150 to 270° C. When an improvedprocessability of the polymer composition is desired, it is morepreferred that the melting temperature is 260° C. or lower. Theabove-mentioned polyamide resins can be used individually or incombination.

The polycarbonate resin used as component (D) in the present inventionis a polymer which can be obtained by the reaction between a divalent orpolyvalent phenolic compound and a carbonate precursor. There are avariety of divalent phenolic compounds; for example,2,2-bis(4-hydroxyphenyl)propane (so-called “bisphenol A”),bis(4-hydroxyphenyl)methane,2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane,2,2-bis(4-hydroxy-3-methyl-phenyl)propane, bis(4-hydroxyphenyl)sulfone,1,1-bis(4-hydroxyphenyl)ethane, 1,1-bis(4-hydroxyphenyl) cyclohexane and1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane. Preferred examplesof divalent phenolic compounds include bis(4-hydroxyphenyl)alkanes,especially bisphenol A. These divalent phenolic compounds can be usedindividually or in combination. With respect to the carbonate precursor,for example, there can be mentioned a carbonyl halide, a carbonyl esterand a haloformate. More specifically, the carbonate precursor is atleast one member selected from the group consisting of phosgene,diphenyl carbonate and a dihaloformate of a divalent phenolic compound.

The viscosity average molecular weight of the polycarbonate resin usedin the present invention is preferably 10,000 or more, from theviewpoint of improving the strength and heat resistance of the polymercomposition. From the viewpoint of improving the processability of thepolymer composition, it is preferred that the viscosity averagemolecular weight of the polycarbonate resin is 60,000 or less, moreadvantageously from 12,000 to 45,000, still more advantageously from13,000 to 35,000. In the present invention, the viscosity averagemolecular weight (M) is calculated from the specific viscosity value, asmeasured with respect to a solution obtained by dissolving 0.7 g of thepolycarbonate resin in 100 ml of a methylene chloride at 20° C.

The polyurethane resin used as component (D) in the present invention isobtained by a polyaddition reaction between a diisocyanate and a dioland contains, for example, a polymer block (as a soft segment)comprising a polyol (i.e., polyester or polyether) and a polymer block(as a hard segment) comprising a diisocyanate and a glycol. Examples ofpolyester diols used as a raw material for the polyurethane resininclude poly(1,4-butylene adipate), poly(1,6-hexane adipate) andpolycaprolactone. On the other hand, examples of polyether diols used asa raw material for the polyurethane resin include polyethylene glycol,polypropylene glycol and polyoxytetramethylene glycol. Examples ofglycols used as a raw material for the polyurethane resin includeethylene glycol, 1,4-butanediol and 1,6-hexanediol. Examples ofdiisocyanates used as a raw material for the polyurethane resin includearomatic diisocyanates, alicyclic diisocyanates and aliphaticdiisocyanates, such as toluylene diiusocyanate, 4,4′-diphenylmethanediisocyanate, hexamethylene diisocyanate and isophorone diisocyanate.

The weight average molecular weight of the polyurethane resin used inthe present invention is preferably in the range of from 5,000 to500,000, more preferably from 10,000 to 300,000, from the viewpoint ofobtaining a polymer composition which exhibits excellent mechanicalproperties.

Examples of thermoplastic resins other than the functionalgroup-containing thermoplastic resins which can be used as component (D)in the present invention include a block copolymer of a conjugated dienemonomer and a vinyl aromatic hydrocarbon monomer; a polymer of theabove-mentioned vinyl aromatic hydrocarbon monomer; a copolymer of theabove-mentioned vinyl aromatic hydrocarbon monomer with at least onevinyl monomer (other than the vinyl aromatic hydrocarbon monomer), suchas ethylene, propylene, butylene, vinyl chloride and vinylidenechloride; a rubber-modified styrene resin (HIPS); ethylene polymers,such as polyethylene, a copolymer of ethylene with a comonomercopolymerizable with ethylene, which has an ethylene content of 50% byweight or more (e.g., an ethylene/propylene copolymer, anethylene/butylene copolymer, an ethylene/hexene copolymer or anethylene/octene copolymer,) and a chlorinated polyethylene; propylenepolymers, such as polypropylene, a copolymer of propylene with acomonomer copolymerizable with propylene, which has a propylene contentof 50% by weight or more (e.g., a propylene/ethylene copolymer) and achlorinated polypropylene; butene polymers, such as a polybutene resinand a copolymer of 1-butene with a comonomer copolymerizable with1-butene, which has a 1-butene content of 50% by weight or more; vinylchloride polymers, such as a polyvinyl chloride resin, a polyvinylidenechloride resin and a copolymer of vinyl chloride and/or vinylidenechloride with at least one comonomer copolymerizable with vinyl chlorideand/or vinylidene chloride, which has a vinyl chloride and/or vinylidenechloride content of 50% by weight or more; polymeric straight chainhydrocarbon compounds in which all or part of the hydrogen atoms in thehydrocarbon compound is replaced by a fluorine atom, such asfluororesins (e.g., polytetrafluoroethylene,tetrafluoroethylene/perfluoroalkylvinylether copolymer,tetrafluoroethylene/hexafluoropropylene copolymer,polychlorotrifluoroethylene, tetrafluoroethylene/ethylene copolymer,chlorotrifluoroethylene/ethylene copolymer, polyvinylidene fluoride andpolyvinyl fluoride) and polybutadiene resins, such as 1,2-polybutadieneand trans-polybutadiene. The number average molecular weight of theabove-mentioned thermoplastic resins is preferably 1,000 or more, morepreferably in the range of from 5,000 to 5,000,000, still morepreferably in the range of from 10,000 to 1,000,000. These thermoplasticresins can be used individually or in combination.

Examples of rubbery polymers usable as component (D) include aconjugated diene rubber and a hydrogenation product thereof (other thanthe modified polymer (A) of the present invention); a random copolymerrubber produced from a conjugated diene monomer and a vinyl aromatichydrocarbon monomer and a hydrogenation product thereof (other than themodified polymer (A) of the present invention); a block copolymer rubberproduced from a conjugated diene monomer and a vinyl aromatichydrocarbon monomer and a hydrogenation product thereof (other than themodified polymer (A) of the present invention); a polymer rubbercontaining one or no double bond; and a natural rubber. Specificexamples of such rubbery polymers include a butadiene rubber and ahydrogenation product thereof; an isoprene rubber and a hydrogenationproduct thereof; styrene type elastomers, such as a styrene/butadienerubber and a hydrogenation product thereof (other than the modifiedhydrogenated copolymer (a) of the present invention), astyrene/butadiene block copolymer and a hydrogenation product thereofand a styrene/isoprene block copolymer and a hydrogenation productthereof; and acrylonitrile/butadiene rubber and a hydrogenation productthereof. Specific examples of a polymer rubber containing one or nodouble bond include olefin type elastomers, such as anethylene/propylene rubber, an ethylene/propylene/diene rubber, anethylene/butene/diene rubber, an ethylene/butene rubber, anethylene/hexene rubber and an ethylene/octene rubber; a butyl rubber; abrominated butyl rubber; an acrylic rubber; a fluororubber; a siliconerubber; a chlorinated polyethylene rubber; an epichlorohydrin rubber; anα, β-unsaturated nitrile/acrylic ester/conjugated diene copolymerrubber; a urethane rubber and a polysulfide rubber. Each of theserubbery polymers may be modified by introducing thereto a functionalgroup (thereby obtaining a functional group-containing rubbery polymer).The above-mentioned rubbery polymers can be used individually or incombination.

Examples of functional group-containing rubbery polymer include arubbery polymer having bonded thereto a group containing at least onefunctional group selected from the group consisting of a hydroxyl group,a carboxyl group, a carbonyl group, a thiocarbonyl group, an acid halidegroup, an acid anhydride group, a carboxylic acid group, athiocarboxylic acid group, an aldehyde group, a thioaldehyde group, acarbonic ester group, an amide group, a sulfonic acid group, a sulfonicester group, a phosphate group, a phosphoric ester group, an aminogroup, an imino group, a nitrile group, a pyridyl group, a quinolinegroup, an epoxy group, a thioepoxy group, a sulfide group, an isocyanategroup, an isothiocyanate group, a silanol group, an alkoxysilane, ahalogenated silica group, a halogenated tin group, an alkoxytin groupand a phenyltin group.

With respect to the amounts of component (A) and component (D) which isat least one member selected from the group consisting of thethermoplastic resin and the rubbery polymer, the component (A)/component(D) weight ratio is in the range of from 1/99 to 99/1, preferably from2/98 to 90/10, more preferably from 5/95 to 60/40, still more preferablyfrom 10/90 to 40/60. The component (A)/component (D) weight ratio may beappropriately determined so that the modified polymer compositionexhibits the advantageous properties of each component at a maximumlevel.

Further, it is preferred that the modified polymer composition of thepresent invention further comprises 0.01 to 20 parts by weight, relativeto 100 parts by weight of the total of components (A) and (D), of (C) amodifier having a functional group which is reactive to the functionalgroup of the modifier group of the modified polymer (A), wherein themodifier (C) is at least one member selected from the group consistingof a functional monomer and a functional oligomer. When component (A) isthe first-order modified, hydrogenated polymer (A-1) or the first-ordermodified polymer (A-3), a second-order modifier can be added to thecomposition so that the polymer contained in the final compositionbecomes a second-order modified polymer. When component (A) is thesecond-order modified polymer (A-2), a third-order modifier can be addedto the composition so as to further modify the second-order modifiedpolymer contained in the final composition. The above-mentionedfunctional monomers and functional oligomers can be used as thesecond-order modifier or the third-order modifier. From the viewpoint ofmechanical strength and impact resistance of the modified polymercomposition, the amount of the modifier (C) is 0.01 part by weight ormore, relative to 100 parts by weight of the total of components (A) and(D). From the viewpoint of obtaining the desired effect, the amount ofthe modifier (C) is 20 parts by weight or less, relative to 100 parts byweight of the total of components (A) and (D). The amount of themodifier (C) is preferably 0.02 to 10 parts by weight, more preferably0.05 to 7 parts by weight, relative to 100 parts by weight of the totalof components (A) and (D).

In the present invention, if desired, an additive may be added to themodified polymer composition. With respect to the additive, there is noparticular limitation, and any additives which are conventionally usedin thermoplastic resins or rubbery polymers can be used. Specificexamples of additives include reinforcing fillers (B), silane couplingagents and rubber softening agents mentioned above; inorganic fillers;pigments; lubricants; mold release agents; softening agents andplasticizers; antioxidants, such as a hindered phenol type antioxidantand a phosphorus type thermal stabilizer; hindered amine type lightstabilizers; benzotriazole type ultraviolet absorbers; flame retardants;antistatic agents; reinforcing agents, such as an organic fiber, a glassfiber, a carbon fiber and a metal whisker; coloring agents; mixturesthereof; and the additives as described in “Gomu Purasuchikku HaigouYakuhin (Additives for Rubber and Plastic)” (Rubber Digest Co., Ltd.,Japan).

With respect to the method for producing the modified polymercomposition of the present invention, there is no particular limitation,and any of the conventional methods can be employed. For example, themodified polymer composition of the present invention can be produced bymelt-kneading method using a conventional mixing machine, such as aBanbury mixer, a single-screw extruder, a twin-screw extruder, aco-kneader, a multi-screw extruder, or a method in which the componentsfor the composition are added to a solvent, to thereby obtain a solutionor dispersion of a mixture of the components in the solvent, followed byheating to remove the solvent. From the viewpoint of productivity of thecomposition and uniform mixing of the components of the composition, itis preferred to use the melt-kneading method using an extruder.

<4> Crosslinked, Modified Polymer Composition

The present invention provides a crosslinked, modified polymercomposition obtained by subjecting the modified polymer composition ofitem <3> above to melt-kneading in the presence of a vulcanizing agent.

The crosslinked, modified polymer composition of the present inventionis a composition prepared by the so-called “dynamic crosslinking”method. The thermoplastic resin and/or the rubbery polymer used ascomponent (D) of the modified polymer composition can be vulcanizedtogether with the modified polymer in the presence of a vulcanizingagent or, alternatively, component (D) can be added to a modifiedpolymer after performing the dynamic crosslinking of the modifiedpolymer.

The dynamic crosslinking method used in the present invention is amethod in which components (including a crosslinking agent) for adesired crosslinked product are melt-kneaded at a temperature at which acrosslinking reaction occurs, so as to effect the mixing of componentsand the crosslinking reaction simultaneously. The details of this methodare described in A. Y. Coran et al., Rub. Chem. and Technol. vol. 53,pp. 141-(1980). In the dynamic crosslinking method, the crosslinkingreaction is performed by using an enclosed kneader, such as a Banburymixer or a pressurizing kneader, or a single-screw or twin-screwextruder. The kneading is generally conducted at 130 to 300 ° C.,preferably 150 to 250° C., for 1 to 30 minutes.

In the dynamic crosslinking method, any of the vulcanizing agentsexemplified in item <2> above can be used as the vulcanizing agent, andan organic peroxide or a phenol resin type crosslinking agent isgenerally used. Further, a vulcanization accelerator, an auxiliaryvulcanizing agent and a multifunctional vinyl monomer exemplified initem <2> above can be used in combination with the vulcanizing agentduring the dynamic crosslinking.

In the present invention, the amount of the vulcanizing agent isgenerally in the range of from 0.01 to 15 parts by weight, preferablyfrom 0.04 to 10 parts by weight, relative to 100 parts by weight of thetotal of components (A) and (D).

The crosslinked composition of the present invention, if desired, mayfurther contain an additive mentioned in item <3> above so long as theproperties of the crosslinked composition are not harmfully affected.For example, a softening agent may be used for controlling the hardnessand fluidity of the final product. Specific examples of softening agentsinclude a paraffinic process oil, a naphthenic process oil and/or anaromatic process oil; a mineral oil type softening agent, such as aliquid paraffin; a castor oil and a linseed oil. The amount of thesoftening agent is generally in the range of from 10 to 200 parts byweight, preferably 10 to 150 parts by weight, more preferably 20 to 100parts by weight, relative to 100 parts by weight of component (A).

In the present invention, the reinforcing fillers which are exemplifiedas component (B) in item <1> above may be added to the crosslinked,modified polymer composition of the present invention. The amount of thereinforcing filler is generally in the range of from 0 to 200 parts byweight, preferably from 10 to 150 parts by weight, more preferably from20 to 100 parts by weight, relative to 100 parts by weight of component(A). The reinforcing filler (B) may be used in combination with thesilane coupling agent which is exemplified in item <1> above. The amountof the silane coupling agent is generally in the range of from 0.1 to30% by weight, preferably from 0.5 to 20% by weight, more preferablyfrom 1 to 15% by weight, based on the weight of the reinforcing filler(B).

In the present invention, it is recommended that the dynamiccrosslinking in the modified polymer composition in the presence of avulcanizing agent is performed so that the content of gel (exclusive ofinherently insoluble components, such as the inorganic filler) is 5 to80% by weight, preferably 10 to 70% by weight, more preferably 20 to 60%by weight, based on the weight of the crosslinked product. The gelcontent is determined by the following method. A sample (1 g) of acrosslinked product is refluxed in a Soxhlet's extractor for 10 hoursusing boiled xylene. The resultant residue is filtered through an80-mesh wire mesh. The dry weight (g) of the insoluble matters remainingon the filter is measured, and the ratio (% by weight) of the obtaineddry weight to the weight of the sample is calculated. The obtained ratiois defined as the gel content of the crosslinked product.

<5> Adhesive Composition

The present invention provides an adhesive composition comprising:

-   -   100 parts by weight of component (A) selected from the group        consisting of the first-order modified, hydrogenated polymer        (A-1) of the present invention, the second-order modified        polymer (A-2) of the present invention and a first-order        modified polymer (A-3) which is a precursor of the        above-mentioned second-order modified polymer, and    -   20 to 400 parts by weight of (E) a tackifier. The adhesive        composition prepared using the modified polymer of the present        invention exhibits an excellent balance of adhesive properties        (such as adhesion strength and adhesion retention).

With respect to component (E) (i.e., the tackifier) used to produce theadhesive composition of the present invention, there is no particularlimitation, and it is possible to use any conventional tackifyingresins, such as a rosin type terpene resin, a hydrogenated rosin typeterpene resin, a hydrogenated terpene resin, a coumarone resin, aphenolic resin, a terpene/phenol resin, an aromatic hydrocarbon resinand an aliphatic hydrocarbon resin. These tackifiers can be usedindividually or in combination. Specific examples of tackifiers includethose which are described in the above-mentioned “Gomu PurasuchikkuHaigou Yakuhin (Additives for Rubber and Plastic)” (published by RubberDigest Co., Ltd., Japan). The amount of the tackifier is generally from20 to 400 parts by weight, preferably from 50 to 350 parts by weight,relative to 100 parts by weight of component (A) (i.e., a modifiedpolymer). When the amount of the tackfier is less than 20 parts byweight, it is unlikely that the adhesive composition exhibitssatisfactory adhesion. On the other hand, when the amount of thetackfier is more than 400 parts by weight, the adhesion retention of theadhesive composition is likely to become lowered. Therefore, in eithercase, the adhesion properties of the adhesive composition tend to beimpaired.

It is preferred that the adhesive composition of the present inventionfurther comprises 0.01 to 20 parts by weight of (C) a modifier having afunctional group which is reactive to the functional group of themodifier group of the modified polymer (A), wherein the modifier (C) isat least one member selected from the group consisting of a functionalmonomer and a functional oligomer. When component (A) is the first-ordermodified, hydrogenated polymer (A-1) or the first-order modified polymer(A-3), a second-order modifier can be added to the composition so thatthe polymer contained in the final composition becomes a second-ordermodified polymer. When component (A) is the second-order modifiedpolymer (A-2), a third-order modifier can be added to the composition soas to further modify the second-order modified polymer contained in thefinal composition. The above-mentioned functional monomers andfunctional oligomers can be used as the second-order modifier or thethird-order modifier.

The adhesive composition may contain a conventional softening agent,such as a naphthenic process oil, a paraffinic process oil, or a mixturethereof. The addition of a softening agent to the adhesive compositionis advantageous in that the viscosity of the adhesive composition isreduced, so that the processability and adhesion property of theadhesive composition are improved. The amount of the softening agent isin the range of from 10 to 200 parts by weight, relative to 100 parts byweight of the modified polymer (A). When the amount of the softeningagent is more than 200 parts by weight, the adhesion retention of theadhesive composition tends to be markedly impaired.

Further, if desired, the adhesive composition may contain a stabilizer,such as an antioxidant or a light stabilizer.

Also, the adhesive composition may contain at least one member selectedfrom the group consisting of pigments (such as red iron oxide andtitanium dioxide); waxes (such as a paraffin wax, a microcrystalline waxand a low molecular weight polyethylene wax); thermoplastic resins (suchas polyolefin thermoplastic resins (e.g., amorphous polyolefin and anethylene/ethylacrylate copolymer) and low molecular weight vinylaromatic hydrocarbon thermoplastic resins); natural rubbers; syntheticrubbers, such as a polyisoprene rubber, a polybutadiene rubber, astyrene/butadiene rubber, an ethylene/propylene rubber, a chloroprenerubber, an acrylic rubber, an isoprene/isobutylene rubber, apolypentenamer rubber, a styrene/butadiene block copolymer and astyrene/isoprene block copolymer, and may also contain the hydrogenationproducts of the above-mentioned block copolymers.

With respect to the method for producing the adhesive composition, thereis no particular limitation. For example, the adhesive composition canbe produced by a method in which the above-mentioned components for theadhesive composition are uniformly mixed using a conventional mixer orkneader while heating.

The adhesive composition of the present invention has excellent balancebetween various adhesion properties, such as adhesion strength andadhesion retention. By virtue of these excellent properties, theadhesive composition can be advantageously used as a material for anadhesive tape and label, a pressure-sensitive lamina, apressure-sensitive sheet, a surface protection sheet and film; a backadhesive for fixing a lightweight plastic shaped article, a backadhesive for fixing a carpet or tile, and an adhesive. Especially, theadhesive composition can be advantageously used as a material for anadhesive tape, an adhesive sheet and film, an adhesive label, a surfaceprotection sheet and film, and an adhesive.

<6> Asphalt Composition

The present invention provides an asphalt composition comprising:

-   -   0.5 to 50 parts by weight of component (A) selected from the        group consisting of the first-order modified, hydrogenated        polymer (A-1) of the present invention, the second-order        modified polymer (A-2) of the present invention, and a        first-order modified polymer (A-3) which is a precursor of the        above-mentioned second-order modified polymer, and    -   100 parts by weight of (F) an asphalt. The asphalt composition        comprising the modified polymer of the present invention        exhibits excellent properties with respect to ductility,        flexural properties and adhesion.

Examples of asphalts (F) for use in the asphalt composition of thepresent invention include a petroleum asphalt (i.e., asphalt by-producedby oil refining), a mixture thereof with petroleum, natural asphalt, anda mixture thereof with petroleum. Each of the above-mentioned asphaltscontains bitumen as the main component thereof. Specific examples ofasphalts include a straight asphalt, a semi-blown asphalt, a blownasphalt, tar, pitch, a cutback asphalt (i.e., a mixture of asphalt withoil), and an asphalt emulsion. These asphalts can be used incombination. As a preferred asphalt (F), there can be mentioned astraight asphalt having a penetration ratio of from 30 to 300,preferably from 40 to 200, more preferably from 45 to 150. The amount ofcomponent (A) contained in the asphalt composition is generally from 0.5to 50 parts by weight, preferably from 1 to 30 parts by weight, morepreferably from 3 to 20 parts by weight, relative to 100 parts by weightof the asphalt contained in the asphalt composition.

It is preferred that the asphalt composition of the present inventionfurther comprises (C) a modifier having a functional group which isreactive to the functional group of the modifier group of the modifiedpolymer (A), wherein the modifier (C) is at least one member selectedfrom the group consisting of a functional monomer and a functionaloligomer. The modifier (C) is used in an amount of from 0.01 to 5 partsby weight, preferably from 0.05 to 5 parts by weight, more preferablyfrom 0.1 to 5 parts by weight, still more preferably from 0.2 to 3 partsby weight, still more preferably from 0.5 to 2 parts by weight, relativeto 100 parts by weight of the asphalt. When component (A) is thefirst-order modified, hydrogenated polymer (A-1) or the first-ordermodified polymer (A-3), a second-order modifier can be added to thecomposition so that the polymer contained in the final compositionbecomes a second-order modified polymer. When component (A) is thesecond-order modified polymer (A-2), a third-order modifier can be addedto the composition so as to further modify the second-order modifiedpolymer contained in the final composition. The above-mentionedfunctional monomers and functional oligomers can be used as thesecond-order modifier or the third-order modifier.

The asphalt composition of the present invention comprising components(A) and (F) (i.e., the asphalt), may further comprise 0.1 to 5 parts byweight of component (D) (which is at least one polymer selected from thegroup consisting of a thermoplastic resin other than component (A) and arubbery polymer other than component (A)), relative to 100 parts byweight of component (F) (i.e., an asphalt).

If desired, the asphalt composition of the present invention comprisingcomponent (A), an asphalt (F) and modifier (C) may contain asulfur-containing component. As a sulfur-containing component, there canbe used, for example, a powdery sulfur, a precipitated sulfur, acolloidal sulfur, a surface-treated sulfur, an insoluble sulfur and aninert sulfur. Further examples of a sulfur-containing component includea sulfur-containing compound, such as sulfur chloride, sulfur dioxide,morpholine disulfide, an alkylphenol disulfide and a high-molecularweight polysulfide. Also, the sulfur-containing component can be used incombination with an appropriate amount of a crosslinking accelerator. Asa crosslinking accelerator, there can be used a sulfenamide typeaccelerator, a guanidine type accelerator, a thiuram type accelerator,an aldehyde-amine type accelerator, an aldehyde-ammonia typeaccelerator, a thiazole type accelerator, a thiourea type accelerator, adithiocarbamate type accelerator and a xanthate type accelerator.Specific examples of such crosslinking accelerators include adiphenylguanidine, n-butyl aldehyde-anil condensate, ahexamethylenetetramine, 2-mercaptobenzothiazole,N-cyclohexyl-2-benzothiazyl sulfenamide, thiocarbanilide,tetramethylthiuram monosulfide, sodium dimethyl dithiocarbamate and zincisopropyl xanthogenate. The amount of the sulfur-containing component isgenerally in the range of from 0.01 to 10 parts by weight, preferablyfrom 0.05 to 5 parts by weight, more preferably from 0.1 to 2 parts byweight, relative to 100 parts by weight of component (F) (i.e., anasphalt). When the crosslinking accelerator is used, the amount ofcrosslinking accelerator is generally in the range of from 0.01 to 10parts by weight, preferably from 0.05 to 5 parts by weight, morepreferably from 0.1 to 2 parts by weight, relative to 100 parts byweight of component (F) (i.e., an asphalt).

The asphalt composition of the present invention may contain a silanecoupling agent. As a silane coupling agent, the silane coupling agentsmentioned in item <1> above can be used. The silane coupling agent isused generally in an amount of from 0.01 to 20 parts by weight,preferably from 0.05 to 10 parts by weight, more preferably from 0.1 to5 parts by weight, relative to 100 parts by weight of component (F)(i.e., an asphalt).

From the viewpoint of obtaining an asphalt composition which exhibitsexcellent aggregate-gripping properties, the asphalt composition of thepresent invention may contain a surfactant, such as an anionicsurfactant, a cationic surfactant and a nonionic surfactant. Specificexamples of surfactants include a higher fatty acid and a metal saltthereof, a monoamine compound, a diamine compound, a polyamine compoundand a co-oligomer of polyethylene oxide and polypropylene oxide. Furtherexamples of surfactants include an acidic, organic phosphate compound; amixture of an acidic, organic phosphate compound and an inorganicphosphate compound; a polyvalent carboxylic acid or an anhydridethereof; an aliphatic phosphate; a phosphoric acid ester with a higheralcohol (e.g., stearyl phosphate); a mixture of a higher alcohol and aphosphorylated alcohol; gallic acid or derivatives thereof; fatty acidsderived from a tall oil, or derivatives thereof; a condensate ofpolyalkylenepolyamine and a fatty acid; a liquid epoxy; a graft-modifiedpolyethylene obtained by grafting maleic anhydride onto polyethylene; agraft-modified polypropylene obtained by grafting maleic anhydride ontopolypropylene; a graft-modified SBS (styrene/butadiene block copolymer)obtained by grafting maleic anhydride onto SBS; a graft-modified SEBS(styrene/ethylene/butylene block copolymer) obtained by grafting maleicanhydride onto SEBS; and a graft-modified SEPS(styrene/ethylene/propylene block copolymer) obtained by grafting maleicanhydride onto SEPS.

If desired, the asphalt composition of the present invention may containany of the conventional additives. There is no limitation with respectto the type of the additive so long as it is an additive which isgenerally used in combination with a thermoplastic resin or a rubberycopolymer. Examples of conventional additives include component (B)(i.e., the reinforcing filler), an inorganic filler other than component(B), an organic filler, a rubber-softening agent, a tackifier, astabilizer (e.g., antioxidant), a vulcanizing agent (e.g., an organicperoxide or a phenol resin crosslinking agent), an auxiliary for use inperoxide crosslinking, a polyfunctional vinyl monomer, and other variousadditives as mentioned above. If desired, component (D) (i.e., theabove-mentioned thermoplastic resin or rubbery polymer) may be used asan additive.

The asphalt composition of the present invention exhibits excellentproperties with respect to, e.g., softening temperature, ductility,flexural properties, aggregate-gripping properties and storage stabilityat high temperatures. Hence, the asphalt composition can beadvantageously used in a wide variety of fields, such as the fields of amaterial for use in road paving, a material for a waterproof sheet, amaterial for a noise insulation sheet and a roofing material.

The asphalt composition of the present invention is especially useful inthe field of drainage pavements. By virtue of its excellent propertieswith respect to storage stability at high temperatures, ductility,flexural properties at low temperatures and aggregate-grippingproperties, the asphalt composition of the present invention can beadvantageously used as a binder for a drainage pavement for variousroads, for example, a road having a large traffic, an expressway, and aroad segment at which the load of traffic tends to concentrate (e.g., anintersection or a curving road). When the asphalt composition of thepresent invention is used as a binder for a drainage pavement, theobtained drainage pavement exhibits excellent properties with respectto, e.g., rutting resistance, water permeability, traffic noisereduction properties and low-temperature properties (e.g., crackresistance at low temperatures).

Generally, an asphalt pavement is formed by the following method. To amixture of a coarse aggregate (e.g., crushed stone), a fine aggregate(e.g., sand or crushed sand), stone dust and the like (wherein themixture has an appropriate range of particle size distribution), isadded a binder which is heated, to thereby obtain an asphalt mixture.The obtained asphalt mixture is spread over a road, and the resultantasphalt mixture layer on the road is rolled flat by using a roller orthe like, to thereby obtain an asphalt pavement. On the other hand, thedrainage pavement layer of the drainage pavement produced using theasphalt composition of the present invention has an extremely largenumber of intercommunicating voids for drainage, as compared to thenumber of voids in the pavement layer of the conventional pavementproduced using a conventional asphalt mixture. By virtue of suchproperty, the drainage pavement produced using the asphalt compositionof the present invention exhibits excellent functions, e.g., thedrainability for preventing the occurrence of rain pools, the ability toensure safe driving by preventing a continuous water thin layer frombeing formed by rain on the road, and the ability to reduce trafficnoise (e.g., an exhaust noise or a noise caused by the contact betweenrotating tires and the road surface). The asphalt composition of thepresent invention can be advantageously used in producing a drainagepavement layer of the drainage pavement, wherein the drainage pavementlayer has a void fraction of from 5 to 35%, more advantageously from 10to 30%, still more advantageously from 12 to 28%.

There is no particular limitation with respect to the method forproducing the asphalt composition of the present invention, and theasphalt composition can be produced by melt-kneading an asphalt and themodified polymer of the present invention, together with variousoptional components, by using a conventional mixing machine, such as amelting vessel, a kneader, a Banbury mixer and an extruder.

<7> Styrene Resin Composition

The present invention provides a styrene resin composition obtained bysubjecting a raw material mixture to radical polymerization, the rawmaterial mixture comprising:

-   -   2 to 30 parts by weight, relative to 100 parts by weight of the        total of components (A) and (G), of component (A) selected from        the group consisting of the first-order modified, hydrogenated        polymer (A-1) of the present invention, the second-order        modified polymer (A-2) of the present invention, and a        first-order modified polymer (A-3) which is a precursor of the        above-mentioned second-order modified polymer, and    -   98 to 70 parts by weight, relative to 100 parts by weight of the        total of components (A) and (G), of (G) a vinyl aromatic        hydrocarbon monomer or a mixture of a vinyl aromatic hydrocarbon        monomer and a comonomer copolymerizable with the vinyl aromatic        hydrocarbon monomer.

The raw material mixture used for producing the styrene resincomposition of the present invention may further comprise (C) a modifierhaving a functional group which is reactive to the functional group ofthe modifier group of the modified polymer (A), wherein the modifier (C)is at least one member selected from the group consisting of afunctional monomer and a functional oligomer. When component (A) is thefirst-order modified, hydrogenated polymer (A-1) or the first-ordermodified polymer (A-3), a second-order modifier can be added to thecomposition so that the polymer contained in the final compositionbecomes a second-order modified polymer. When component (A) is thesecond-order modified polymer (A-2), a third-order modifier can be addedto the composition so as to further modify the second-order modifiedpolymer contained in the final composition. The above-mentionedfunctional, monomers and functional oligomers can be used as thesecond-order modifier or the third-order modifier.

In the present invention, from the viewpoint of mechanical properties ofthe styrene resin composition, the modifier (C) is used in an amount of0.01 part by weight or more, relative to 100 parts by weight ofcomponent (A). For achieving the effects of addition of the modifier,the modifier (C) is used in an amount of 20 parts by weight or less,relative to 100 parts by weight of component (A). It is preferred thatthe amount of the modifier (C) is in the range of from 0.02 to 10 partsby weight, more advantageously from 0.05 to 7 parts by weight, relativeto 100 parts by weight of component (A).

The styrene resin composition of the present invention can be producedas follows. A raw material mixture is prepared by either dissolving ordispersing the components of the styrene resin composition, such as amodified polymer (A), a modifier (C) and a reinforcing filler (B) incomponent (G) which is a vinyl aromatic hydrocarbon monomer or a mixtureof a vinyl aromatic hydrocarbon monomer and a comonomer copolymerizablewith the vinyl aromatic hydrocarbon monomer, to thereby obtain a rawmaterial mixture. The obtained raw material mixture is subjected tograft polymerization while stirring so as to apply shearing stress tothe raw material mixture, thereby obtaining a styrene resin composition.The graft polymerization is performed by bulk polymerization, bulksuspension polymerization or solution polymerization. The thus obtainedstyrene resin composition is a styrene resin composition having astructure wherein a graft polymer particles are dispersed in a polymermatrix, wherein the polymer matrix is made of a vinyl aromatichydrocarbon polymer or a copolymer of a vinyl aromatic hydrocarbonmonomer and a comonomer copolymerizable with the vinyl aromatichydrocarbon monomer, and the graft polymer particles are made of a graftpolymer obtained by grafting a vinyl aromatic hydrocarbon monomer or amonomer component which is a mixture of a vinyl aromatic hydrocarbonmonomer and a comonomer copolymerizable with the vinyl aromatichydrocarbon monomer onto the modified polymer or a hydrogenation productthereof. In the present invention, the styrene resin composition maycontain a modified polymer (A) which is not grafted with a vinylaromatic hydrocarbon monomer or a monomer component which is a mixtureof a vinyl aromatic hydrocarbon monomer and a comonomer copolymerizablewith the vinyl aromatic hydrocarbon monomer.

Examples of vinyl aromatic hydrocarbon monomers used in the presentinvention include styrene; vinylnaphthalene; α-alkyl substitutedstyrenes, such as α-methylstyrene, α-ethylstyrene andα-methyl-p-methylstyrene; nuclear- and alkyl-substituted styrenes, suchas m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene,ethylvinylbenzene and p-tert-butylstyrene; halogenated styrenes, such asmonochlorostyrene, dichlorostyrene, tribromostyrene andtetrabromostyrene; p-hydroxystyrene and o-methoxystyrene. These vinylaromatic hydrocarbon monomers can be used individually or incombination. Of these, styrene, α-methylstyrene and p-methylstyrene arepreferred.

As a comonomer copolymerizable with the vinyl aromatic hydrocarbonmonomer, there can be mentioned an unsaturated nitrile monomer, a(meth)acrylic acid ester and the like. The amount of the comonomercopolymerizable with the vinyl aromatic hydrocarbon monomer contained inthe mixture of the vinyl aromatic hydrocarbon monomer and the comonomeris 10 to 90% by weight, preferably 20 to 80% by weight, based on theweight of the mixture.

Specific examples of unsaturated nitrites include acrylonitrile andmethacrylonitrile. These unsaturated nitriles can be used individuallyor in combination. Of these, acrylonitrile is especially preferred.

Specific examples of (meth)acrylic acid esters include methylacrylate,ethylacrylate, propylacrylate, butylacrylate, amylacrylate,hexylacrylate, octylacrylate, dodecylacrylate, cyclohexylacrylate,methylmethacrylate, ethylmethacrylate, propylmethacrylate,butylmethacrylate, amylmethacrylate, hexylmethacrylate,octylmethacrylate, dodecylmethacrylate and cyclohexylmethacrylate. These(meth)acrylic acid esters can be used individually or in combination. Ofthese, methylmethacrylate is especially preferred.

Specific examples of other comonomers copolymerizable with the vinylaromatic hydrocarbon monomer include acrylic acid, methacrylic acid,vinyl acetate, maleic anhydride, N-methylmaleimide andN-phenylmaleimide.

During the production of the styrene resin composition of the presentinvention, the graft polymerization may be performed after adding aninert solvent to component (G) which is selected from the groupconsisting of a vinyl aromatic hydrocarbon monomer and a mixture of avinyl aromatic hydrocarbon monomer and a comonomer copolymerizable withthe vinyl aromatic hydrocarbon monomer. Examples of inert solventsinclude polar solvents, such as ethylbenzene, toluene, methyl ethylketone and cyclohexanone, and these solvents can be used individually orin combination. The amount of the inert solvent is preferably 100 partsby weight or less, more preferably 50 parts by weight or less, relativeto 100 parts by weight of monomer component (G).

In the present invention, the radical polymerization of a raw materialmixture comprising a vinyl aromatic hydrocarbon monomer or a mixture ofa vinyl aromatic hydrocarbon monomer and a comonomer copolymerizablewith the vinyl aromatic hydrocarbon monomer, a modified polymer or ahydrogenation product thereof, and a reinforcing filler may be performedin the presence of an organic peroxide or an azo compound. Graftpolymerization reaction is more likely to occur in the presence of anazo compound and, therefore, a styrene resin composition havingexcellent properties can be obtained by the use of an azo compound.

Specific examples of organic peroxides include peroxyketals, such as1,1-bis(tert-butylperoxy)cyclohexane and1,1-bis(tert-butylperoxy)-3,3,5-trimethyl-cyclohexane; dialkylperoxides, such as di-t-butyl-peroxide,2,5-dimethyl-2,5-di(tert-butylperoxy)hexane and dicumyl peroxide; diacylperoxides, such as benzoyl peroxide, m-toluoyl peroxide and lauroylperoxide; peroxydicarbonates, such as dimyristylperoxydicarbonate anddiisopropylperoxydicarbonate; peroxyesters, such ast-butylperoxyisopropylcarbonate, t-butylperoxyacetate,di-t-butyldiperoxyisophthalate and t-butylperoxybenzoate; ketoneperoxides, such as cyclohexanone peroxide and methyl ethyl ketoneperoxide; and hydroperoxides, such as p-mentha hydroperoxide, t-butylhydroperoxide and cumene hydroperoxide. Specific examples of azocompounds include azobisisobutylonitrile and azobiscyclohexanecarbonitrile. These compounds can be used individually or incombination. The amount of the organic peroxide or the azo compound ispreferably in the range of from 10 to 1000 ppm, relative to the amountof component (G) (i.e., a monomer component).

Further, use can be made of a conventional chain transfer agent.Specific examples of the chain transfer agents include mercaptanes, suchas n-dodecylmercaptane and tert-dodecylmercaptane; α-methylstyrenedimer; terpenes, such as 1-phenylbutene-2-fluorene and dipentene; andhalogenated compounds, such as chloroform. The amount of the chaintransfer agent is in the range of from 5 to 5000 ppm, relative to theamount of component (G) (i.e., a monomer component).

In the present invention, the above-mentioned reinforcing filler (B) maybe contained in the styrene resin composition. The amount of thereinforcing filler (B) is in the range of from 0.5 to 300 parts byweight, preferably from 1 to 200 parts by weight, more preferably from 5to 100 parts by weight, relative to 100 parts by weight of component (A)(i.e., a modified polymer). When the amount of the reinforcing filler(B) contained in a styrene resin composition is less than 0.5 part byweight, the effect of adding the reinforcing filler becomesunsatisfactory. On the other hand, when the amount of the reinforcingfiller (B) contained in a styrene resin composition is more than 300parts by weight, the processability and the mechanical strength of sucha styrene resin composition becomes poor.

For promoting the interaction between the modified polymer (A) and thereinforcing filler (B), use can be made of a silane coupling agenthaving a group which exhibits an affinity or bonding ability to eitheror both of the modified polymer (A) and the reinforcing filler (B). As asilane coupling agent, those exemplified above can be used. The amountof the silane coupling agent is in the range of from 0.1 to 30% byweight, preferably 0.5 to 20% by weight, more preferably 1 to 15% byweight, based on the weight of the reinforcing filler (B). The effectsof using the silane coupling agent can not be obtained when the amountof the silane coupling agent is less than 0.1% by weight, and no furtherimprovements are achieved by using more than 30% by weight of the silanecoupling agent.

Further, the present invention provides a method for producing a styreneresin composition, comprising:

-   -   (1) providing a raw material mixture comprising (A) the modified        polymer, (G) a vinyl aromatic hydrocarbon monomer or a mixture        of a vinyl aromatic hydrocarbon monomer and a comonomer        copolymerizable with the vinyl aromatic hydrocarbon monomer, and        optionally at least one member selected from the group        consisting of (C) a modifier and (B) a reinforcing filler, and    -   (2) subjecting the raw material mixture to radical        polymerization,    -   thereby obtaining a styrene resin composition.

When a raw material mixture is prepared by either dissolving ordispersing the components of the styrene resin composition, such as amodified polymer (A), a modifier (C) and a reinforcing filler (B) incomponent (G), there can be mentioned a method in which each of amodified polymer (A) and a reinforcing filler (B) are individuallydissolved or dispersed in component (G); a method in which each of amodified polymer (A), a reinforcing filler (B) and a modifier (C) areindividually dissolved or dispersed in component (G); a method in whicha modified polymer (A) and a reinforcing filler (B) are mixed in asolvent or melt-kneaded using a conventional mixing machine, such as aBanbury mixer, a roll, a kneader, a single-screw extruder, a twin-screwextruder or a multi-screw extruder, to thereby obtain a modified resincomposition, and the obtained modified resin composition is dissolved ordispersed in component (G); and a method in which a modified polymer(A), a reinforcing filler (B) and a modifier (C) are mixed in a solventor melt-kneaded using a conventional mixing machine, such as a Banburymixer, a roll, a kneader, a single-screw extruder, a twin-screw extruderor a multi-screw extruder, to thereby obtain a modified resincomposition, and the obtained modified resin composition is dissolved ordispersed in component (G).

The styrene resin composition of the present invention may furthercontain conventional stabilizers, such as an antioxidant and anultraviolet light stabilizer. Examples of antioxidants includeoctadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate,2,6-di-t-butyl-4-methylphenol,2-(1-methylcyclohexyl)-4,6-dimethylphenol,2,2′-methylene-bis(4-ethyl-6-t-butyl-phenol),4,4′-thio-bis(6-t-butyl-3-methylphenol),2,4-bis[(octylthio)methyl]-o-cresol, triethyleneglycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate],tris(dinonylphenyl)phosphite, tris-(2,4-di-t-butylphenyl)phosphite. Theamount of the antioxidant is in the range of from 0.01 to 5 parts byweight, preferably 0.1 to 2 parts by weight, relative to 100 parts byweight of the styrene resin composition.

Specific examples of ultraviolet light stabilizers include triazole typeultraviolet light stabilizers, such as2-(5-methyl-2-hydroxyphenyl)benzotriazole and2-(3,5-di-t-butyl-2-hydroxyphenyl)benzotriazole; hindered amine typeultraviolet light stabilizers, such asbis(2,2,6,6-tetramethyl-4-piperidyl)sebacate; p-t-butylphenylsalicylateand 2,2′-dihydroxy-4-methoxy-benzophenone. Especially preferred aretriazole type and hindered amine type ultraviolet light stabilizers, andthese ultraviolet light stabilizers can be used individually or incombination. The ultraviolet light stabilizer is preferably used in anamount in the range of from 0.01 to 5 parts by weight, more preferablyfrom 0.05 to 2 parts by weight, relative to 100 parts by weight of thestyrene resin composition.

In addition, if desired, a conventional internal lubricant used in thisfield (such as a liquid paraffin, a mineral oil and anorganopolysiloxane) may be added to the styrene resin composition. Forexample, 0.005 to 10 parts by weight of polydimethylsiloxane (which isan organopolysiloxane) may be added to 100 parts by weight of a styreneresin composition.

The gelation ratio (i.e., content of components which are insoluble intoluene) of the styrene resin composition produced by the method of thepresent invention is preferably in the range of from 5 to 75% by weight,more preferably from 10 to 50% by weight. When the gelation ratio islower than 5% by weight, the impact resistance of such a styrene resincomposition becomes poor, and when the gelation ratio is too high, thefluidity becomes lowered and such a styrene resin composition aredisadvantageous for producing molded articles. In addition, the swellingindex of the styrene resin composition measured using toluene (i.e.,weight of the composition swelled with toluene/dry weight after removingtoluene) is preferably in the range of from 5 to 15, more preferablyfrom 7 to 12. When the swelling index is lower than 5, the impactresistance becomes poor, and when the swelling index is more than 12,the impact resistance and luster becomes poor. The swelling index can becontrolled by adjusting the final reaction rate of the graftpolymerization reaction of the comonomer components (which reaction isperformed by bulk polymerization, bulk suspension polymerization orsolution polymerization) and the volatilization temperature of theunreacted comonomer(s).

The weight average molecular weight of the resin forming the matrix ispreferably in the range of from 70,000 to 500,000, more preferably from100,000 to 300,000. The weight average molecular weight is measured bygel permeation chromatography (GPC) using standard polystyrene samples.When the weight average molecular weight is less than 70,000, such astyrene resin composition has low impact resistance, and when the weightaverage molecular weight is more than 500,000, such a styrene resincomposition has too low fluidity to produce molded articles todisadvantage.

In the present invention, especially preferred styrene resin compositionis a styrene resin composition having a structure wherein a graftpolymer particles are dispersed in a polymer matrix and all or part ofthe reinforcing filler (B) are present in the dispersion phase of thegraft polymer particles or in the vicinity thereof, wherein the polymermatrix is made of a vinyl aromatic hydrocarbon polymer or a copolymer ofa vinyl aromatic hydrocarbon monomer and a comonomer copolymerizablewith the vinyl aromatic hydrocarbon monomer, and the graft polymerparticles are made of a graft polymer obtained by grafting a vinylaromatic hydrocarbon monomer or a monomer component which is a mixtureof a vinyl aromatic hydrocarbon monomer and a comonomer copolymerizablewith the vinyl aromatic hydrocarbon monomer onto the modified polymer.The styrene resin composition of the present invention having theabove-mentioned structure has an excellent balance of impact resistance,stiffness and luster.

If desired, a flame retardant and an auxiliary flame retardant may beadded to the styrene resin composition of the present invention toimpart flame retardancy to the final molded articles. Various types offlame retardants are known in the art and any conventional flameretardant can be used. Examples of flame retardants include a halogentype flame retardant, a phosphorus type flame retardant, a hydroxidetype flame retardant and a silicon type flame retardant. Specificexamples of flame retardants include decabromodiphenyl oxide,tetrabromobisphenol A, a tetrabromobisphenol A oligomer,tris(2,3-dibromopropyl-1) isocyanurate, ammonium phosphate, redphosphorus, tricresyl phosphate, magnesium hydroxide and aluminumhydroxide. As an auxiliary flame retardant, there can be mentionedantimony trioxide, antimony pentoxide, sodium antimonate, antimonytrichloride, antimony pentachloride, zinc borate, barium metaborate andzirconium oxide.

Further, if desired, various additives, such as a lubricant, a moldrelease agent, a filler, an antistatic agent and a coloring agent can beadded to the styrene resin composition. Further, other thermoplasticresins, such as a general purpose polystyrene, an acrylonitrile/styrenecopolymer resin (AS), an acrylonitrile/butadiene/styrene copolymer resin(ABS), an acrylonitrile/ethylenepropylene/styrene copolymer resin (AES);a methacrylonitrile/butadiene/styrene copolymer resin (MBS); apolyphenylene ether, a polycarbonate, a styrene/butadiene copolymer, amethylmethacrylate/styrene copolymer resin, a maleic anhydride/styrenecopolymer resin, a polyamide resin and a polyester resin, can be addedto the styrene resin composition.

The thermoplastic resins are used to impart advantageous properties,such as heat resistance, stiffness, impact resistance, appearance andcoating properties, and one or more thermoplastic resins are selectedbased on the desired properties of the styrene resin composition.

The styrene resin composition can be advantageously used as variousshaped articles produced by a method, such as an injection molding andan extrusion molding. The shaped articles can be used in various fields,such as cabinets and housings of home electric appliances and officeautomation apparatuses; interior or exterior parts of automobiles; partsof buildings and furnitures; and parts of antenna for broadcasting andcommunication.

BEST MODE FOR CARRYING OUT THE INVENTION

Hereinbelow, the present invention will be described in more detail withreference to the following Reference Examples, Examples and ComparativeExamples, which should not be construed as limiting the scope of thepresent invention.

The characteristics and properties of the base polymers, first-ordermodified polymers and the second-order modified polymers were determinedby the following methods.

(1) Styrene Content

The absorption intensity of a polymer at 262 nm was measured using anultraviolet spectrophotometer (trade name: UV-2450; manufactured andsold by Shimadzu Corporation, Japan), and the styrene content wascalculated therefrom.

(2) Styrene Block Ratio

A predetermined amount (from 30 to 50 mg) of an unhydrogenated blockcopolymer was precisely weighed and added to about 10 ml of chloroform.To the resultant were added osmium tetraoxide (as a catalyst) andtertiary butyl hydroperoxide (as an oxidant) to obtain a mixture. Theobtained mixture was boiled at 100° C. for 20 minutes to effect anoxidative degradation of the block copolymer, thereby obtaining areaction mixture. To the obtained reaction mixture was added methanol inan amount of 200 ml to precipitate a polystyrene, thereby obtaining aprecipitate. The obtained precipitate was filtered using 11G4(manufactured and sold by SHIBATA SCIENTIFIC TECHNOLOGY LTD., Japan) toobtain a filtration residue comprised of a polystyrene. (However, thepolymer chains having an average polymerization degree of 30 or lesswere not taken into consideration in the measurement of the styreneblock ratio.) The polystyrene obtained as the filtration residue wasweighed, and a styrene block ratio was calculated from the followingformula:

Styrene block ratio (wt %) (weight of the filtration residue/weight ofstyrene monomer units in the above-mentioned predetermined amount of theblock copolymer)×100.

(3) Vinyl Bond Content and Hydrogenation Ratio

The vinyl bond content and hydrogenation ratio were measured by means ofa nuclear magnetic resonance (NMR) apparatus (trade name: DPX-400;manufactured and sold by BRUKER, Germany).

(4) Mooney Viscosity

The Mooney viscosity was measured by means of a Mooney viscometer inaccordance with JIS K 6300, under conditions wherein the testtemperature was 100° C., preheating time was 1 minute, rotation was 2rpm, and the test time was 4 minutes.

(5) Weight Average Molecular Weight and Molecular Weight Distribution

The weight average molecular weight was measured by gel permeationchromatography (GPC) (GPC apparatus: LC10; column: ShimpacGPC805+GPC804+GPC804+GPC803; both of the apparatus and column aremanufactured and sold by Shimadzu Corporation, Japan) under conditionswherein tetrahydrofuran was used as a solvent and the column temperaturewas 35° C. The weight average molecular weight was determined from a GPCchromatogram showing the peak molecular weight, using a calibrationcurve obtained with respect to the peak molecular weights ofcommercially available monodisperse standard polystyrene samples.

(6) Ratio of Modified Polymer Fractions in a Modified Polymer

A sample solution was prepared by mixing together 20 ml oftetrahydrofuran, 10 mg of a modified polymer and 10 mg of a lowmolecular weight internal standard polystyrene having a weight averagemolecular weight of 8,000. The sample solution was subjected to gelpermeation chromatography (GPC) in the same manner as in item (5) above,to thereby obtain a chromatogram. From the chromatogram, the ratio (a)of the peak area of the modified polymer (containing unmodified polymerfractions) to the peak area of the internal standard polystyrene wasdetermined.

On the other hand, the same sample solution as mentioned above wassubjected to gel permeation chromatography (GPC) in substantially thesame manner as in item (5) above, except that there was used a columnpacked with a silica gel (tradename: Zorbax, manufactured and sold byDuPont, U.S.A). The silica gel adsorbs the modified polymer fractions,but does not adsorb the unmodified polymer fractions. From the resultantchromatogram, the ratio (b) of the peak area of the polymer (i.e.,unmodified polymer fractions) to the peak area of the internal standardpolystyrene was determined. Thus, the ratio (a) reflects the total peakarea ascribed to both the unmodified polymer fractions and the modifiedpolymer fractions, and the ratio (b) reflects the peak area ascribed toonly the unmodified polymer fractions. Therefore, from the differencebetween the ratios (a) and (b), the ratio of the modified polymerfractions in the modified polymer was obtained.

The hydrogenation catalysts and base polymers used for producing thefirst-order modified, hydrogenated polymer and second-order modifiedpolymer of the present invention were prepared by the following method.

1. Preparation of a Hydrogenation Catalyst

(1) Hydrogenation Catalyst I:

A reaction vessel was purged with nitrogen. To the reaction vessel wasadded one liter of dried, purified cyclohexane, followed by addition of100 mmol of bis(η⁵-cyclopentadienyl)titanium dichloride. Whilethoroughly stirring the resultant mixture in the reaction vessel, ann-hexane solution of 200 mmol of trimethylaluminum was added to thereaction vessel, and a reaction was effected at room temperature forabout 3 days to thereby obtain hydrogenation catalyst I.

(2) Hydrogenation Catalyst II:

A reaction vessel was purged with nitrogen. To the reaction vessel wereadded two liters of dried, purified cyclohexane. Then, 40 mmol ofbis(η⁵-cyclo-pentadienyl)titanium di-(p-tolyl) and 150 g of1,2-polybutadiene having a molecular weight of about 1,000 (wherein the1,2-polybutadiene had a 1,2-vinyl bond content of about 85%) were addedto and dissolved in the cyclohexane, thereby obtaining a solution. Acyclohexane solution of 60 mmol of n-butylithium was added to thesolution in the reaction vessel, and a reaction was effected at roomtemperature for 5 minutes and, then, 40 mmol of n-butanol wasimmediately added to the reaction vessel while stirring, therebyobtaining hydrogenation catalyst II. The obtained hydrogenation catalystII was preserved at room temperature.

2. Preparation of a Living Polymer used as a Base Polymer for Producingthe Modified Polymers of the Present Invention

Preparation of Polymer 1:

A living polymer was produced by performing a continuous polymerizationby the following method in which a reaction vessel which has an internalvolume of 10 liters and is equipped with a stirrer and a jacket wasused. An n-hexane solution which contained, as monomers forcopolymerization, butadiene and styrene (butadiene/styrene weight ratio:82/18; total concentration of the butadiene and styrene monomers: 16% byweight), and a cyclohexane solution of 1% by weight of n-butylithium (asa polymerization initiator) were fed to the reaction vessel at rates of157 g/min and 4.1 g/min, respectively. Further, an n-hexane solution of1% by weight of N,N,N′,N′-tetramethylethylenediamine (as a polarsubstance) was fed to the reaction vessel at a rate of 2 g/min, tothereby perform a continuous polymerization at 86° C., thereby obtaininga solution of polymer 1 (P-1) which was a living copolymer. Thecharacteristics of polymer 1 (P-1) are shown in Table 1.

Preparation of Polymer 2:

Polymer 2 (P-2) (which was a living copolymer) was obtained insubstantially the same manner as in the preparation of polymer 1 (P-1),except that the amount of n-butylithium fed to the reaction vessel waschanged as indicated in Table 1. The characteristics of polymer 2 areshown in Table 1.

Preparation of Polymer 3:

A living polymer was produced by performing a continuous polymerizationby the following method in which a reaction vessel which has an internalvolume of 10 liters and is equipped with a stirrer and a jacket wasused. An n-hexane solution which contained, as monomers forcopolymerization, butadiene and styrene (butadiene/styrene weight ratio:65/35; total concentration of the butadiene and styrene monomers: 16% byweight), and a cyclohexane solution of 1% by weight of n-butylithium (asa polymerization initiator) were fed to the reaction vessel at rates of157 g/min and 4.2 g/min, respectively. Further, an n-hexane solution of1% by weight of 2,2-bis(2-oxolanyl)propane (as a polar substance) wasfed to the reaction vessel at a rate of 2.2 g/min, to thereby perform acontinuous polymerization at 83° C., thereby obtaining a solution ofpolymer 3 (P-3) which was a living copolymer. The characteristics ofpolymer 3 (P-3) are shown in Table 1.

Preparation of Polymer 4:

Polymer 4 (P-4) (which was a living copolymer) was obtained insubstantially the same manner as in the preparation of polymer 3 (P-3),except that the amount of n-butylithium fed to the reaction vessel waschanged as indicated in Table 1. The characteristics of polymer 4 areshown in Table 1.

Preparation of Polymer 5:

A living polymer was produced by performing a continuous polymerizationby the following method in which two reaction vessels (i.e., a firstreaction vessel and a second reaction vessel) were used, each of whichhas an internal volume of 10 liters (the L/D=4, wherein L represents theinner height of the reaction vessel and D represents the inner diameterof the reaction vessel) and is equipped with a stirrer and a jacket. Acyclohexane solution of butadiene (butadiene concentration: 24% byweight), a cyclohexane solution of styrene (styrene concentration: 24%by weight), and a cyclohexane solution of n-butylithium (which solutioncontained 0.11 g of n-butylithium, relative to 100 g of the total of themonomers for copolymerization (i.e., the total of the above-mentionedbutadiene and styrene) were fed to the bottom portion of the firstreaction vessel at rates of 7.07 liters/hr, 3.47 liters/hr and 20liters/hr, respectively. Further, a cyclohexane solution ofN,N,N′,N′-tetramethylethylenediamine was fed to the bottom portion ofthe first reaction vessel at a rate wherein the amount ofN,N,N′,N′-tetramethylethylenediamine fed to the first reaction vesselwas 0.44 mole, per mole of the n-butylithium, to thereby perform acontinuous polymerization at 90° C. The reaction temperature wasadjusted by controlling the jacket temperature. The temperature aroundthe bottom portion of the first reaction vessel was about 88° C. and thetemperature around the top of the first reaction vessel was about 90° C.The average residence time of a polymerization reaction mixture in thefirst reaction vessel was about 45 minutes. The conversion of butadienewas approximately 100% and the conversion of styrene was approximately99%.

From the first reaction vessel, a copolymer solution was withdrawn andfed to the bottom portion of the second reaction vessel. Simultaneouslywith the feeding of the copolymer solution, a cyclohexane solution ofstyrene (styrene concentration: 24% by weight) was fed to the bottomportion of the second reaction vessel at a rate of 2.31 liters/hr. Inthe second reaction vessel, a continuous polymerization was performed at90° C. to thereby obtain a solution of polymer 5 (P-5) which was aliving copolymer. The characteristics of polymer 5 (P-5) are shown inTable 1.

Preparation of Polymer 6:

Polymer 6 (P-6) (which was a living copolymer) was obtained insubstantially the same manner as in the preparation of polymer 5 (P-5),except that the feeding rate of the cyclohexane solution of butadiene tothe first reaction vessel was changed to 4.51 liters/hr, the feedingrate of the cyclohexane solution of styrene to the first reaction vesselwas changed to 5.97 liters/hr, and the feeding rate of the cyclohexanesolution of styrene to the second reaction vessel was changed to 2.38liters/hr. The characteristics of polymer 6 (P-6) are shown in Table 1.

Preparation of Polymers 7 and 8:

Polymers 7 and 8 (P-7 and P-8) (each of polymers 7 and 8 was a livingpolymer) were obtained in substantially the same manner as in thepreparation of polymer 1, except that the amounts of n-butylithium fedto the reaction vessel was changed as indicated in Table 1 and styrenewas not used as a monomer for polymerization. The characteristics ofpolymers 7 and 8 (P-7 and P-8) are shown in Table 1.

Preparation of Polymer 9:

A living polymer was produced by performing a polymerization by thefollowing method in which a reaction vessel which has an internal volumeof 10 liters and is equipped with a stirrer and a jacket was used. Thereaction vessel was charged with 510 g of butadiene, 390 g of styrene,5,500 g of cyclohexane and 0.70 g of 2,2-bis(2-oxolanyl)propane (as apolar substance) and the temperature of the reaction vessel wasmaintained at 30° C. To the resultant reaction vessel was charged acyclohexane solution containing 0.95 g of n-butylithium (as apolymerization initiator), to thereby initiate the polymerizationreaction. After the start of the polymerization reaction, the innertemperature of the reaction vessel increased gradually due to the heatof polymerization reaction. 100 g of butadiene was further added to thereaction vessel in 5 minutes at a feeding rate of 20 g/min, wherein thefeeding was initiated at a point in time of 7 minutes from the additionof the polymerization initiator and terminated at 12 minutes from theaddition of the polymerization initiator. The inner temperature of thereaction vessel finally reached 75° C. As a result, solution of apolymer 9 (P-9), which was a living copolymer, was obtained. Thecharacteristics of polymer 9 (P-9) are shown in Table 1.

Preparation of Polymer 10:

Polymer 10 (P-10) was obtained in substantially the same manner as inthe preparation of polymer 9 (P-9), except that the amount ofn-butylithium fed to the reaction vessel was changed as indicated inTable 1. The characteristics of polymer 9 are shown in Table 1.

Preparation of Polymer 11:

A living polymer was produced by performing a polymerization by thefollowing method in which a reaction vessel which has an internal volumeof 10 liters and is equipped with a stirrer and a jacket was used. Thereaction vessel was charged with 530 g of butadiene, 470 g of styrene,5,500 g of cyclohexane and 0.1 g of 2,2-bis(2-oxolanyl)propane (as apolar substance). To the resultant reaction vessel was charged acyclohexane solution containing, as a polymerization initiator, 1.2 g ofn-butylithium, to thereby initiate the polymerization reaction. Afterthe start of the polymerization reaction, the inner temperature of thereaction vessel increased gradually due to the heat of polymerizationreaction. The inner temperature of the reaction vessel finally reached75° C. As a result, a solution of polymer 11 (P-11), which was a livingcopolymer, was obtained. The characteristics of polymer 11 (P-11) areshown in Table 1.

Preparation of Polymers 12 and 13:

Polymers 12 and 13 (P-12 and P-13) (each of polymers 12 and 13 was aliving copolymer) were obtained in substantially the same manner as inthe preparation of polymer 11, except that the amount of the polarsubstance used was changed to 0.3 g and 0.09 g for producing polymers 12and 13, respectively. Further, the amounts of the monomers forcopolymerization and n-butylithium charged into the reaction vessel werechanged as indicated in Table 1. The characteristics of polymers 12 and13 (P-12 and P-13) are shown in Table 1.

Preparation of Polymer 14:

A living polymer was produced by performing a polymerization by thefollowing method in which a reaction vessel which has an internal volumeof 10 liters and is equipped with a stirrer and a jacket was used. Thereaction vessel was charged with 900 g of butadiene and 5,500 g ofcyclohexane, and the inner temperature of the reaction vessel wasmaintained at 40° C. To the resultant reaction vessel was charged acyclohexane solution containing 0.855 g of n-butylithium (as apolymerization initiator), to thereby initiate the polymerizationreaction. After the start of the polymerization reaction, the innertemperature of the reaction vessel increased gradually due to the heatof polymerization reaction. The inner temperature of the reaction vesselfinally reached 75° C. As a result, a solution of polymer 14 (P-14),which was a living polymer, was obtained. The characteristics of polymer14 (P-14) are shown in Table 1.

EXAMPLES 1 TO 18 AND 70, REFERENCE EXAMPLES 1 TO 14 AND COMPARATIVEEXAMPLES 1 TO 4

A first-order modified, unhydrogenated polymer was obtained using theliving polymers indicated in Table 1 and the first-order modifiersindicated in Table 2. Specifically, to the living polymer solutions wereindividually added predetermined amounts of first-order modifiers asindicated in Table 2, and a reaction was performed at 70° C. for 20minutes, thereby obtaining reaction mixtures respectively containingfirst-order modified, unhydrogenated polymers.

A first-order modified, hydrogenated polymer was obtained byhydrogenating the above-obtained first-order modified, unhydrogenatedpolymer using the above-mentioned hydrogenation catalyst I orhydrogenation catalyst II. Specifically, to a reaction mixturecontaining a first-order modified, unhydrogenated polymer was addedhydrogenation catalyst I or hydrogenation catalyst II in an amount of100 ppm in terms of the amount of titanium, relative to 100 parts byweight of the first-order modified, unhydrogenated polymer. Ahydrogenation reaction was performed for 1 hour under conditions whereinthe hydrogen pressure was 0.7 MPa and the reaction temperature was 65°C., thereby obtaining a reaction mixture containing a first-ordermodified, hydrogenated polymer.

The first-order modified, unhydrogenated polymer and the first-ordermodified, hydrogenated polymer obtained above were purified as follows.To the reaction mixtures respectively containing the first-ordermodified, unhydrogenated polymers and first-order modified, hydrogenatedpolymers were individually added methanol in a molar amount which is 10times the molar amount of n-butylithium used in the polymerizationreaction. Then, carbonated water was added to the resultant, so as toadjust the pH value of the resultant to pH 8 or less. To each of theresultant reaction mixtures was added, as a stabilizer,octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate in an amount of0.3 part by weight, relative to 100 parts by weight of the polymer,followed by steam stripping to thereby distill off the solvent in thereaction mixture. The resultant polymer was dehydrated and dried, tothereby obtain a first-order modified, unhydrogenated polymer or afirst-order modified, hydrogenated polymer.

The characteristics of the thus obtained first-order modified,unhydrogenated polymer and the first-order modified, hydrogenatedpolymer are shown in Table 2.

EXAMPLES 19 TO 21, 23 TO 34, 36 TO 43 AND 71

Preparation of a Second-Order Modified Polymer

The first-order modified, hydrogenated polymer and a first-ordermodified, unhydrogenated polymer obtained in Examples 1 to 18 and 70 andReference Examples 1 to 13 were individually reacted with a second-ordermodifier in accordance with the formulations indicated in Table 3,thereby obtaining second-order modified polymers. To the first-ordermodified, hydrogenated polymers (prepared in the Examples) and thefirst-order modified, unhydrogenated polymers (prepared in the ReferenceExamples) were individually added predetermined amounts of second-ordermodifiers (a functional monomer or a functional oligomer) as indicatedin Table 3. The resultant mixtures were individually kneaded by means ofan enclosed kneader (internal volume: 1.7 liters) which has two rotorsand is equipped with a temperature control device employing acirculating water. The kneading was performed under conditions whereinthe packing ratio was 65%, the revolution rate of two rotors were 66 rpmand 77 rpm, respectively, to effect a reaction, thereby obtainingsecond-order modified polymers. Alternatively, the resultant mixtureswere individually melt-kneaded and extruded by means of a 30 mm φtwin-screw extruder under conditions wherein the cylinder temperaturewas 220° C. and the screw revolution rate was 100 rpm, to effect areaction, thereby obtaining second-order modified polymers.

EXAMPLE 22

To the reaction mixture containing the first-order modified,unhydrogenated polymer 1P-9 (obtained in Example 9), which was obtainedby adding a first-order modifier to a solution of a living polymer, wasadded methanol in a molar amount which is 10 times the molar amount ofn-butylithium used in the polymerization reaction. Then, carbonatedwater was added to the resultant, so as to adjust the pH value of theresultant to pH 8 or less. To the resultant mixture was added apredetermined amount of a second-order modifier (a functional monomer)as indicated in Table 3, and a reaction was performed at about 60° C.for 30 minutes. To the resultant reaction mixture was added, as astabilizer, octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate in anamount of 0.3 part by weight, relative to 100 parts by weight of thepolymer, followed by steam stripping to thereby distill off the solventin the reaction mixture. The resultant polymer was dehydrated and dried,to thereby obtain second-order modified polymer 2P-4.

EXAMPLE 35

To the reaction mixture containing the first-order modified polymer1P-23 (obtained in Reference Example 5), which was obtained by adding afirst-order modifier to a solution of a living polymer, was added apredetermined amount of a second-order modifier (a functional monomer)as indicated in Table 3, and a reaction was performed at about 60° C.for 30 minutes. Then, carbonated water was added to the resultant, so asto adjust the pH value of the resultant to pH 8 or less. To theresultant reaction mixture was added, as a stabilizer,octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate in an amount of0.3 part by weight, relative to 100 parts by weight of the polymer,followed by steam stripping to thereby distill off the solvent in thereaction mixture. The resultant polymer was dehydrated and dried, tothereby obtain second-order modified polymer 2P-17.

The compositions of the present invention are explained in the followingExamples and Comparative Examples.

Crosslinked, Filler-Containing Modified Polymer Composition

The properties of the crosslinked, filler-containing modified polymercompositions (obtained in the Examples) and the crosslinked,filler-containing unmodified polymer compositions (obtained in theComparative Examples) were measured and evaluated by the followingmethods.

(1) Bound Rubber Content

A sample of a kneaded polymer composition (0.2 g) was cut into squares(about 1 mm×1 mm) and placed in a Harris container (a wire meshcontainer, 100-mesh). The weight of the resultant polymer compositionsample was precisely weighed. The container containing the polymercomposition sample was immersed in toluene for 24 hours to therebydissolve the rubber components which are not bound to the reinforcingfiller. The container was taken out from toluene and the insolublematerial remaining inside the container was taken out and driedcompletely. The weight of the dried insoluble material was weighed, tothereby determine the amount of the insoluble material contained in thepolymer composition sample. The content of the rubber components whichare bound to the reinforcing fillers in the polymer composition wascalculated from the amount of the insoluble material contained in thepolymer composition sample and defined as the bound rubber content ofthe polymer composition.

(2) Viscosity of the Composition

The viscosity was measured using a Mooney viscometer in accordance withJIS K 6300, under conditions wherein the test temperature was 100° C.,preheating time was 1 minute, rotation was 2 rpm, and the test time was4 minutes.

(3) Tensile Strength

Tensile strength was measured in accordance with JIS K6251.

(4) Impact Resilience

The impact resilience was measured by means of a Lupke reboundresilience tester in accordance with JIS K 6255 (in which the impactresilience was measured at 50° C.).

(5) Compression Set

A compression set was measured at 100° C. for 70 hours in accordancewith JIS K 6262.

(6) Viscoelastic Property

The storage modulus (G′) was measured by means of a viscoelasticitytesting apparatus (manufactured and sold by Rheometric Scientific FE,Japan) under torsion mode, wherein the strain at 50° C. was varied from0.01 to 10%. The difference (ΔG′) in the storage modulus G′ value asbetween the strain of 0.1% and the strain of 10% was determined. Thesmaller the ΔG′ value, the better the dispersion properties of silica.

(7) Adhesiveness

The adhesiveness was evaluated by determining the peeling strength (peelangle: 180°) in accordance with JIS K 6256. A test specimen was preparedby adhering a polymer composition onto a metal plate using, as a primer,Metaloc G and Metaloc PH-50 (both manufactured and sold by Toyo KagakuKenkyujyo, Japan).

EXAMPLES 44 TO 51 AND COMPARATIVE EXAMPLES 5 AND 6

Crosslinked, filler-containing modified polymer compositions wereproduced in accordance with the formulations indicated in Tables 4 and 5by the following kneading method. Polymer (A), a silica (reinforcingfiller (B)), an organosilane coupling agent, an oil (a naphtene oil isused when polymer (A) is an unhydrogenated polymer and a parafin oil isused when polymer (A) is a hydrogenated polymer), zinc white, stearicoxide and optionally a sencond-order modifier (C) were kneaded by meansof an enclosed kneader (internal volume: 1.7 liters) which has tworotors and is equipped with a temperature control device employing acirculating water. The kneading was perfromed under conditions whereinthe packing ratio was 65%, the revolution rate of two rotors were 66 rpmand 77 rpm, respectively, thereby obtaining a mixture. The temperatureof the obtained mixture delivered from the kneader was 160° C. Aftercooling the mixture, the cooled mixture was further kneaded with sulfurand a vulcanization accelerator in an open roll at 70° C. The resultantmixture was molded and subjected to vulcanization press to vulcanize themixture, thereby obtaining a crosslinked, filler-containing polymercomposition.

The properties of the obtained crosslinked, filler-containing polymercompositions are shown in Table 5. As apparent from Table 5, silica canbe dispersed uniformly in the crosslinked, filler-containing polymercomposition comprising the modified polymer of the present invention andthese compositions (produced in Examples 44 to 51) exhibit not onlyimproved compression set and impact resilience, but also excellentadhesion, as compared to the compositions of Comparative Examples 5 and6 each comprising an unmodified polymer.

Modified Polymer Composition

The properties of the modified polymer compositions (of the Examples)and the unmodified polymer compositions (of Comparative Examples) wereevaluated by measuring the Izod impact strength in accordance with JISK-7110.

EXAMPLES 51 TO 57 AND COMPARATIVE EXAMPLES 7 AND 8

Modified polymer compositions and unmodified polymer compositions wereproduced in accordance with the formulations indicated in Table 6.Specifically, predetermined amounts of thermoplastic resin (D) andmodified polymer (A), and optionally second-order modifier (C) weredry-blended and the resultant blend product was melt-kneaded to obtain apolymer composition. A polyethylene terephthalate (trade name: MitsuiPET SA135; manufactured and sold by Mitsui Chemicals, Japan) or apolyamide (i.e., nylon 6) (trade name: Amilan CM1017; manufactured andsold by Toray Industries Inc., Japan) was used as the thermoplasticresin (D). The blend product was melt-kneaded and extruded by means of a30 mm φ twin-screw extruder under conditions wherein the screwrevolution rate was 250 rpm. In the melt-kneading, the cylindertemperature of the twin screw-extruder was changed as follows dependingon the thermoplastic resin used: when the thermoplastic resin was a PET,the cylinder temperature was 250° C., and when the thermoplastic resinwas a polyamide, the cylinder temperature was 260° C. In this way,polymer compositions were obtained. The properties of the obtainedcompositions are shown in Table 6. As apparent from Table 6, the polymercomposition comprising the modified polymer of the present inventionexhibited excellent impact resistance as compared to each of thecompositions of Comparative Examples 7 and 8 comprising an unmodifiedpolymer.

Adhesive Composition

The method for measuring the various properties of the adhesivecomposition are as follows.

(1) Melt Viscosity

The melt viscosity of the adhesive composition was measured at 180° C.with a rotation speed of 100 rpm by means of a Brookfield viscometerequipped with a rotor (spindle No. 29).

(2) Softening Point (Ring-and-Ball Method)

The softening point of the adhesive composition was measured inaccordance with JIS K 2207. Specifically, the ring of a ring-and-ballapparatus as defined in JIS K 2207 (which comprises a ring, and aring-supporting member having a bottom plate placed several centimetersbelow the ring) was filled with a sample of the adhesive composition soas to have the sample adhesive composition securely held in the hole ofthe ring. The ring-and-ball apparatus was immersed in water, and thering was maintained level in water. Then, a ball having a weight of 3.5g was placed at the center of the ring filled with the sample. Thetemperature of the water was elevated at a rate of 5° C./min, so as tosoften the sample gradually. The central portion of the softening samplewas gradually sagged under the weight of the ball, and the temperature(softening point) at which the sagged central portion of the samplereached the bottom plate was measured.

(3) Melt Viscosity Change Ratio

The melt viscosity change ratio was measured by means of a Brookfieldviscometer equipped with a rotor (spindle No. 29). The melt viscosity ofthe adhesive composition just after kneading at 180° C. with a rotationspeed of 100 rpm was defined as η₀ and the melt viscosity of theadhesive composition which had been allowed to stand still at 180° C.for 48 hours was defined as η₁. The melt viscosity change ratio wascalculated by the formula below and used as a yardstick for heatstability.Melt viscosity change ratio (%)={(η₁−-η₀)/η₀}×100.(4) Adhesiveness

The adhesive composition in a molten state was coated on a polyesterfilm by means of an applicator, thereby forming an adhesive tape samplehaving a 50 μm-thick adhesive composition layer. Using the adhesive tapesample, the adhesiveness of the adhesive composition was measured asfollows.

The adhesive tape sample having a width of 25 mm was attached to astainless-steel board and, then, peeled therefrom at a peeling rate of300 mm/min to measure a peel strength (peel angle: 180°).

EXAMPLE 58

Polymer (2P-19) (100 parts by weight), a tackifier (E) (trade name:Clearon P-105; manufactured and sold by YASUHARA CHEMICAL CO., LTD.,Japan) (300 parts by weight) and a softening agent (trade name: Dianaprocess oil PW-90; manufactured and sold by Idemitsu Kosan Co., Ltd.,Japan) (100 parts by weight) were melt-kneaded at 180° C. for 2 hours bymeans of a vessel which has a volume of 1 liter and is equipped with astirrer, thereby obtaining a hot-melt type adhesive composition. To theadhesive composition was added, as a stabilizer,butyl-6-(3-t-butyl-2-hydroxy-5-methyl-benzyl)-4-methylphenylacrylate inan amount of 1 part by weight, relative to 100 parts by weight ofpolymer (2P-19).

With respect to the adhesive composition, the melt viscosity (cP at 180°C.) was 10,700 (cP), the softening point was 118° C., the melt viscositychange ratio (%) was 9.0% and the adhesion strength was 1,800 gf/10 mm.

Asphalt Composition

The properties of the asphalt composition were measured by the followingmethods.

(1) Softening Point (Ring-and-Ball Method)

The softening point of the asphalt composition was measured inaccordance with JIS K 2207. Specifically, the ring of a ring-and-ballapparatus as defined in JIS K 2207 (which comprises a ring, and aring-supporting member having a bottom plate placed several centimetersbelow the ring) was filled with a sample of the asphalt composition soas to have the sample asphalt composition securely held in the hole ofthe ring. The ring-and-ball apparatus was immersed in glycerol, and thering was maintained level in glycerol. Then, a ball having a weight of3.5 g was placed at the center of the ring filled with the sample. Thetemperature of the glycerol was elevated at a rate of 5° C./min, so asto soften the sample gradually. The central portion of the softeningsample was gradually sagged under the weight of the ball, and thetemperature (softening point) at which the sagged central portion of thesample reaches the bottom plate was measured.

(2) Elongation

The elongation of an asphalt composition was measured in accordance withJIS K 2207. Specifically, a sample of the asphalt composition was pouredinto a mold to shape the sample in a prescribed form. Then, the shapedsample was placed in a thermostatic vessel and the temperature of thesample was maintained at 15° C. The resultant sample was pulled at arate of 5 cm/min, and the elongation of the sample when the sample wasbroken was measured.

(3) High Temperature Storage Stability

An aluminum can having an internal diameter of 50 mm and a height of 130mm was fully filled with an asphalt composition just after theproduction thereof. The aluminum can containing the asphalt compositionwas placed in an oven and heated at 180° C. for 24 hours. The aluminumcan was taken out from the oven and allowed to stand so that the asphaltcomposition in the aluminum can cooled to room temperature. As samples,upper and lower portions of the resultant solidified asphaltcomposition, which were a 4 cm-thick lower layer at a lower end portionand a 4 cm-thick upper layer at an upper end portion, were taken bycutting. The softening points of both samples were measured. Thedifference in softening point between the samples was used as ayardstick for high temperature storage stability of the asphaltcomposition. The smaller the difference, the better the high temperaturestorage stability of the asphalt composition.

EXAMPLE 59

An asphalt composition having a formulation indicated in Table 7 wasproduced. Specifically, 400 g of straight asphalt 60-80 (manufacturedand sold by NIPPON OIL COMPANY, LIMITED, Japan) was charged into a metalcan having a volume of 750 ml. The metal can containing the straightasphalt was put into an oil bath having a temperature of 180° C. so thatthe straight asphalt was satisfactorily heated, thereby melting theasphalt. Then, to the resultant molten asphalt was added a prescribedamount of the modified polymer (A) bit by bit while stirring. Aftercompletion of addition of the modified polymer (A), the resultantmixture was stirred at a revolution rate of 5,000 rpm for 90 minutes,thereby obtaining an asphalt composition. The properties of the asphaltcomposition are shown in Table 7.

Crosslinked, Modified Polymer Composition

The properties of the crosslinked, modified polymer compositions (of theExamples) and the crosslinked, unmodified polymer compositions (ofComparative Examples) were measured and evaluated by the followingmethods.

(1) Tensile Strength and Tensile Elongation

Tensile strength and tensile elongation were measured in accordance withJIS K6251 (in which a dumbbell No. 3 is used and the tensile stress rate(cross head speed) is 500 mm/min).

(2) Oil Resistance

The oil resistance of a test specimen (50 mm×50 mm, thickness: 2 mm) wasmeasured using test oil No. 3 (a lubricant oil) prescribed in JIS K6301.The test specimen was immersed in the oil at 70° C. for 2 hours and thechange (%) in the weight of the test specimen as between before andafter immersion was determined.

EXAMPLES 60 AND 61 AND COMPARATIVE EXAMPLE 9

In accordance with the formulations indicated in Table 8, the followingcomponents of a polymer composition were mixed using a Henschel mixer,thereby obtaining a mixture.

-   -   Polypropylene resin: Sun Allomer PC600S (manufactured and sold        by Montell SDK Sunrise Ltd., Japan);    -   Paraffin oil: Diana process oil PW380 (manufactured and sold by        Idemitsu Kosan Co., Ltd., Japan);    -   Calcium carbonate: calcium carbonate treated with higher        aliphatic ester;    -   Organic peroxide: PERHEXA 25B (manufactured and sold by NOF        CORPORATION, Japan);    -   Silica: Finely dispersible silica HDK-N200 (manufactured and        sold by WACKER ASAHIKASEI SILICONE CO., Ltd., Japan);    -   Vulcanization accelerator: Divinyl benzene; and    -   Antioxidant: Irganox 1010 (manufactured and sold by Ciba        Speciality Chemicals, Switzerland).

Next, the resultant mixture was melt-kneaded and extruded by means of a30 mm φ twin-screw extruder under conditions wherein the cylindertemperature was 200° C., thereby obtaining a composition prior tovulcanization (step 1). The obtained composition was then subjected to adynamic crosslinking in the following manner. To the obtainedcomposition was added a vulcanizing agent. The resultant mixture wasmelt-kneaded and extruded by means of a 30 mm φ twin-screw extruder at220° C. to effect a vulcanization, thereby obtaining a crosslinkedproduct (step 2). The properties of the crosslinked product are shown inTable 8.

As apparent from Table 8, the crosslinked, modified polymer compositionsof the present invention comprising a modified polymer exhibitsexcellent properties, as compared to the unmodified polymer compositionof Comparative Example 9 which comprises an unmodified polymer.

Styrene Resin Composition

The properties of the styrene resin compositions were measured andevaluated by the following methods.

(1) Notched Izod Impact Strength

The notched Izod impact strength was measured in accordance with K-7110.

(2) Gloss

The gloss of the styrene resin composition was evaluated in accordancewith ASTM D-638, wherein the glossiness (angle of incidence: 60°) of theresin composition was measured at the gate portion and the end portionof a testing device, and the average of the measured values were usedfor evaluating gloss.

(3) Rubber Particle Diameter

The rubber particle diameter of the styrene resin composition isdetermined as follows. A sample of the styrene resin composition isdissolved in dimethylformamide (DMF) under sonication, thereby obtaininga dispersion containing rubbery components. The diameter of the rubberycomponents were measured by means of a Laser scattering particle sizedistribution analyzer (LA-920, manufactured and sold by HORIBA, Ltd.,Japan) and the 50% median diameter was used as rubber particle diameter.

EXAMPLES 62 TO 65 AND COMPARATIVE EXAMPLES 10 AND 11

Styrene resin compositions were individually prepared in accordance withthe formulations indicated in Table 9 by the following bulkpolymerization method. To a reaction vessel equipped with a stirrer anda jacket was added 92 parts by weight of styrene and 8 parts by weightof a modified polymer, followed by addition of 0.3 part by weight ofn-octadecyl-3-(3′,5′di-tert-butyl-4′-hydroxyphenyl)propionate (as astabilizer) and 0.05 part by weight of t-dodecyl mercaptan (as a chaintransfer agent), and the resultant mixture was stirred to thereby obtaina solution. To the obtained solution was added 60 ppm, relative tostyrene monomer contained in the solution, of1,1-bis(tertbutylperoxy)-3,3,5-trimethylcyclohexane, followed by heatingat 105° C. for 3 hours, 120° C. for 2 hours, 150° C. for 2 hours and170° C. for 2 hours in this order to thereby effect a polymerizationreaction. The resultant reaction mixture was further heated at 230° C.for 30 minutes to remove the unreacted monomers under reduced pressure,thereby obtaining a styrene resin composition. The obtained styreneresin composition was pulverized and subjected to extrusion molding,thereby obtaining the styrene resin composition in the form of pellets.The properties of the thus obtained styrene resin composition are shownin Table 9. The styrene resin composition of the present invention hadexcellent impact resistance.

EXAMPLE 66 AND COMPARATIVE EXAMPLE 12

Styrene resin compositions were produced in substantially the samemanner as in Example 62 except that the amounts of styrene andacrylonitrile were changed to 67 parts by weight and 23 parts by weight,respectively. (The thus obtained styrene resin compositions aregenerally called “ABS resins”.) The properties of the obtained styreneresin compositions are shown in Table 9. The ABS resin obtained inExample 66 had excellent impact resistance.

EXAMPLE 67

A styrene resin composition was produced in substantially the samemanner as in Example 62 except that the amounts of styrene andmethylmethacrylate were changed to 42 parts by weight and 48 parts byweight, respectively. (The thus obtained styrene resin composition isgenerally called an “MBS resin”.) The properties of the obtained styreneresin composition is shown in Table 9. The MBS resin obtained in Example67 had excellent impact resistance.

EXAMPLES 68 AND 69 AND COMPARATIVE EXAMPLE 13

In Examples 68 and 69 and Comparative Example 13, with respect to themodified polymers shown in Table 10, the peeling strength was measuredas follows. The modified polymer was formed into a film having athickness of about 100 μm. The polymer film was preheated on a substratefor 5 minutes at a predetermined temperature indicated in Table 10, andthen pressed onto the substrate (load: 1 kg/cm²) for 5 minutes so as toadhere the film onto the substrate (wherein an aluminum plate, a PETfilm and a canvas were individually used as a substrate). Then, theadhered polymer film was peeled off from the substrate at a peeling rateof 200 mm/min. The results of the measurement of the peeling strengthare shown in Table 10. TABLE 1 Living polymer produced Styrene StyreneVinyl bond Polymer Polymerization Amount of n-BuLi used content blockratio content Polymer no. structure* method (g/100 g of monomer) (wt %)(wt %) (%) P-1 C-Li continuous 0.165 18 0 31 P-2 C-Li continuous 0.08418 0 31 P-3 C-Li continuous 0.166 35 0 33 P-4 C-Li continuous 0.085 35 033 P-5 C-S-Li continuous 0.11 45 40 15 P-6 C-S-Li continuous 0.11 67 3016 P-7 B-Li continuous 0.097 0 0 30 P-8 B-Li continuous 0.05 0 0 13 P-9C-Li batch 0.095 39 0 31 P-10 C-Li batch 0.052 39 0 31 P-11 C-S-Li batch0.12 25 45 14 P-12 C-S-Li batch 0.11 47 28 32 P-13 C-S-Li batch 0.085 3543 21 P-14 B-Li batch 0.095 0 0 18*“S” represents a polymer block comprised mainly of styrene monomerunits,“B” represents a polymer block comprised mainly of butadiene monomerunits,“C” represents a copolymer block comprised mainly of styrene monomerunits and butadiene monomer units, and“Li” represents a lithium ion.

TABLE 2 Ratio of Weight First- Hydrogenation modified average orderHydrogenation polymer molecular Polymer modifier* Hydrogenation ratiofractions weight No. Polymer (mol/Li) catalyst (%) (%) (×10⁴) Mw/Mn Ex.1 1P-1 P-1 M2(0.25) I 85 65 30.8 1.8 Ex. 2 1P-2 P-1 M2(0.25) I 95 6530.8 1.8 Ex. 3 1P-3 P-1 M2(0.25) I 71 65 30.8 1.8 Ex. 4 1P-4 P-2 M1(0.9)I 88 67 33.0 1.9 Ex. 5 1P-5 P-3 M3(0.8) II 85 66 32.2 1.9 Ex. 6 1P-6 P-9M2(0.38) II 80 75 33.4 1.4 Ex. 7 1P-7 P-9 M1(0.9) II 85 80 17.1 1.1 Ex.8 1P-8 P-9 M3(0.8) II 85 79 35.5 1.4 Ex. 9 1P-9 P-5 M1(0.9) II 93 5620.0 1.9 Ex. 10 1p-10 P-5 M3(0.8) II 88 53 31.2 2.0 Ref. 1P-11 P-6M1(0.9) II 93 55 20.2 1.9 Ex. 1 Ex. 11 1P-12 P-11 M2(0.38) II 81 81 31.61.3 Ex. 12 1P-13 P-11 M1(0.9) I 82 80 14.6 1.1 Ex. 13 1P-14 P-12M2(0.38) I 80 78 32.0 1.3 Ex. 14 1P-15 P-12 M1(0.9) I 88 79 16.7 1.1 Ex.15 1P-16 P-13 M1(0.9) I 80 77 24.5 1.2 Ex. 16 1P-17 P-7 M1(0.9) I 83 5921.1 2.0 Ex. 17 1P-18 P-8 M1(0.9) I 36 60 29.6 2.3 Ex. 18 1P-19 P-14M2(0.3) I 30 59 35.2 1.2 Ref. 1P-20 P-1 M2(0.4) — — 65 30.8 1.8 Ex. 2Ref. 1P-21 P-2 M1(0.9) — — 67 33.0 1.9 Ex. 3 Ref. 1P-22 P-3 M3(0.8) — —66 32.2 1.9 Ex. 4 Ref. 1P-23 P-4 M1(0.9) — — 68 62.0 2.2 Ex. 5 Ref.1P-24 P-9 M2(0.38) — — 80 49.5 1.4 Ex. 6 Ref. 1P-25 P-5 M3(0.8) — — 5331.2 2.0 Ex. 7 Ref. 1P-26 P-6 M1(0.9) — — 55 20.2 1.9 Ex. 8 Ref. 1P-27P-11 M1(0.9) — — 80 14.6 1.1 Ex. 9 Ref. 1P-28 P-12 M2(0.4) — — 78 32.01.3 Ex. 10 Ref. 1P-29 P-13 M1(0.9) — — 77 24.5 1.2 Ex. 11 Ref. 1P-30 P-8M1(0.9) — — 60 29.6 2.3 Ex. 12 Ref. 1P-31 P-14 M2(0.25) — — 59 35.2 1.2Ex. 13 Ref. 1P-32 P-2 M4(0.9) — — 70 49.7 2.1 Ex. 14 Ex. 70 1P-33 P-3M4(0.9) I 81 68 30.1 1.9 Comp. NP-1 P-2 — — 85 — 33.0 1.9 Ex. 1 Comp.NP-2 P-10 — — — — 28.8 1.1 Ex. 2 Comp. NP-3 P-10 — — 88 — 14.6 1.1 Ex. 3Comp. NP-4 P-6 — — — — 20.1 1.9 Ex. 4*M1: 1,3-dimethyl-2-imidazolidinoneM2: tetraglycidyl-1,3-bisaminomethylcyclohexaneM3: γ-glycidoxypropyltrimethoxysilaneM4: N-(1,3-dimethylbutylidene)-3-(triethoxysilyl)-1-propaneamine

TABLE 3 First- order Second-order Poly- modi- modifier (mol/Li)* merfied Functional Functional No. polymer monomer oligomer Modificationmethod Ex. 19 2P-1 1P-1 D1(1.5) — Melt-kneading method Ex. 20 2P-2 1P-4D2(1.0) — Melt-kneading method Ex. 21 2P-3 1P-4 — D3(1.5) Melt-kneadingmethod Ex. 22 2P-4 1P-9 D1(1.5) — Solution method Ex. 23 2P-5 1P-11D1(1.5) — Melt-kneading method Ex. 24 2P-6 1P-11 — D3(1.5) Melt-kneadingmethod Ex. 25 2P-7 1P-13 D2(1.0) — Melt-kneading method Ex. 26 2P-81P-13 — D3(1.5) Melt-kneading method Ex. 27 2P-9 1P-14 D1(1.5) —Melt-kneading method Ex. 28 2P-10 1P-14 — D3(1.5) Melt-kneading methodEx. 29 2P-11 1P-17 D1(1.5) — Melt-kneading method Ex. 30 2P-12 1P-20D1(1.5) — Melt-kneading method Ex. 31 2P-13 1P-21 D1(1.5) —Melt-kneading method Ex. 32 2P-14 1P-21 D2(1.0) — Melt-kneading methodEx. 33 2P-15 1P-22 D1(1.5) — Melt-kneading method Ex. 34 2P-16 1P-24D1(1.5) — Melt-kneading method Ex. 35 2P-17 1P-23 D1(1.5) — Solutionmethod Ex. 36 2P-18 1P-25 — D3(1.5) Melt-kneading method Ex. 37 2P-191P-26 D1(1.5) — Melt-kneading method Ex. 38 2P-20 1P-27 D1(1.5) —Melt-kneading method Ex. 39 2P-21 1P-27 — D3(1.5) Melt-kneading methodEx. 40 2P-22 1P-28 D1(1.5) — Melt-kneading method Ex. 41 2P-23 1P-29D1(1.5) — Melt-kneading method Ex. 42 2P-24 1P-30 D1(1.5) —Melt-kneading method Ex. 43 2P-25 1P-31 D1(1.5) — Melt-kneading methodEx. 71 2P-26 1P-33 D1(1.5) — Melt-kneading method*D1: maleic anhydrideD2: tetraglycidyl-1,3-bisaminomethylcyclohexaneD3: styrene/maleic anhydride copolymer (Mn 2000)

TABLE 4 Parts by weight Polymer 100 Silica*¹ 50 Second-order modifierFormulation shown in Table 5 Oil*² 20 Silane coupling agent*³ 4 Zincwhite 5 Stearic acid 1 Sulfur 1.5 Vulcanization 1.5 accelerator TT*⁴Vulcanization 0.5 accelerator M*⁵*¹ULTRASIL VN3 (tradename) (manufactured and sold by Degussa Japan,Japan)*²PW-380 (tradename) (a parafin oil, manufactured and sold by IdemitsuKosan, Co. Ltd.; or Shellflex 371N (tradename) (a naphthene oil,manufactured and sold by Shell Chemicals Japan, Japan)*³Silane coupling agent Si69 (manufactured and sold by Degussa Japan,Japan) (chemical nomenclature:bis-[3-(triethoxysilyl)-propyl]-tetrasulfide*⁴chemical nomenclature: tetramethylthiuram disulfide*⁵chemical nomenclature: 2-mercaptobenzothiazole

TABLE 5 Processability Viscosity Properties imparted by AdhesivenessBound of the raw vulcanization (kg/cm) Type Second- rubber materialTensile Impact Compression stainless- of order Formulation contentpolymer strength resilience set Al steel polymer modifier* (mol/Li) (wt%) (100° C.) (MPa) (%) (° C.) ΔG′ plate plate Ex. 44 1P-1 — — 44 78 21.468 15 0.21 8 10 Ex. 45 1P-3 — — 50 70 19.5 68 13 0.19 11 19 Ex. 46 1P-4— — 51 71 25.5 69 12 0.15 9 11 Ex. 47 1P-13 — — 18 88 20.0 68 19 0.92 810 Ex. 48 2P-1 — — 43 90 20.3 69 15 0.4 19 16 Ex. 49 1P-24 D1 1.0 37 13019.5 62 13 2.1 16 19 Ex. 50 2P-16 — — 40 115 21.5 62 11 0.96 17 20 Comp.NP-1 — — 17 91 18.4 61 26 2.6 1 2 Ex. 5 Comp. NP-2 — — 21 88 17.0 58 285.8 2 14 Ex. 6*D1: maleic anhydride

TABLE 6 Formulation (parts by weight) Izod Functional impactgroup-containing Functional Functional strength resin Polymer monomeroligomer (J/m) Ex. 51 PET 80 2P-7 20 — — 300 Ex. 52 PET 80 2P-8 20 — —350 Ex. 53 PET 80 2P-21 20 — — 320 Ex. 54 PET 80 1P-12 20 D2* — 330 Ex.55 polyamide 80 2P-8 20 — — 380 Ex. 56 polyamide 80 2P-21 20 — — 390 Ex.57 polyamide 80 1P-6 20 — D3** 400 Comp. PET 80 NP-3 20 — — 35 Ex. 7Comp. polyamide 80 NP-3 20 — — 40 Ex. 8*D2: tetraglycidyl-1,3-bisaminomethylcyclohexane**D3: styrene/maleic anhydride copolymer (Mn 1000)

TABLE 7 High temperature storage Formu- stability lation (DifferencePolymer of Soft- in Formulation asphalt ening Elonga- softening (parts(parts by point tion point) type by weight) weight) (° C.) (cm) (° C.)Ex. 59 2P-19 8.5 100 86 35 3

TABLE 8 Comp. Ex. 60 Ex. 61 Ex. 9 Formulation Type of polymer 1P-1 1P-1NP-1 of Polymer 100 100 100 crosslinking (parts by weight) compositionSilica 0 20 20 (parts by weight) Polypropylene 40 40 40 (parts byweight) Oil PW380 60 60 60 (parts by weight) Organic peroxide 0.5 0.50.5 (parts by weight) Crosslinking agent 2 2 2 (parts by weight)Properties Tensile strength (MPa) 3.1 5.1 2.0 Tensile elongation (%) 280240 230 Oil resistance (%) 195 92 175

TABLE 9 Comp. Comp. Comp. Ex. Ex. Ex. Ex. Ex. Ex. Ex. Ex. Ex. 62 63 6465 66 67 10 11 12 Formulation Type of polymer 1P-1 1P-1 2P-20 2P-241P-13 1P-16 NP-1 NP-1 NP-3 of Polymer 10   10 10 10 10 10 10 10 10composition (parts by weight) Silica —  1  1 — — — —  1 — (parts byweight) Styrene 90   90 90 90 67 42 90 90 67 (parts by weight)Acrylonitrile — — — — 23 — — — 23 (parts by weight) Methylmethacrylate —— — — — 48 — — — (parts by weight) Properties Rubber particle  1.38   1.35    0.99    1.24    0.87    0.91    0.89    1.02    0.86 diameter(μm) Izod impact strength 17.4    13.6   13.4   16.1   12.1   13.8   8.2  8.5   6.8 (kgcm/cm) Gloss (%) 78   79 86 79 86 82 78 81 78

TABLE 10 Adhesion Peel strength (gf/cm) Type of temperature Al plate PETfilm polymer (° C.) (100 μm) (50 μm) Canvas Ex. 68 1P-9 180 91 68 1650Ex. 69 2P-19 180 210 220 1780 Comp. NP-4 180 28 31 1250 Ex. 13

INDUSTRIAL APPLICABILITY

The first-order modified, hydrogenated polymer and the second-ordermodified polymer of the present invention exhibit strong interactionwith other various components, and by virtue of such property, themodified polymers of the present invention can be advantageously usedfor producing compositions, such as a filler-containing modified polymercomposition, a modified polymer composition comprising a thermoplasticresin and/or a rubbery polymer, an adhesive composition, an asphaltcomposition and a styrene resin composition, which have excellentproperties. In addition, various shaped articles obtained by subjectingthe modified polymer (the first-order modified, hydrogenated polymer andthe second-order modified polymer) and the composition (a polymercomposition comprising the above-mentioned modified polymer and apolymer composition comprising a first-order modified polymer for use asa precursor of the second-order modified polymer) of the presentinvention to extrusion molding, injection molding or the like can beadvantageously used in various fields, such as a material for foodpackages; a material for medical instruments; a raw material for homeelectric appliances and parts thereof, electronic devices and partsthereof, automobile parts, industrial parts, utensils and toys; a rawmaterial for footwear; a raw material for an adhesive; and an asphaltmodifier.

1. A first-order modified, hydrogenated polymer comprising: (1) ahydrogenated polymer obtained by hydrogenating at least oneunhydrogenated polymer selected from the group consisting of (1-A) apolymer comprising conjugated diene monomer units and (1-B) a copolymercomprising conjugated diene monomer units and vinyl aromatic hydrocarbonmonomer units, said copolymer (1-B) having no or at least one polymerblock (H) of said vinyl aromatic hydrocarbon monomer units, and (2) afunctional group-containing first-order modifier group bonded to saidhydrogenated polymer (1), wherein said functional group-containingfirst-order modifier group comprises at least one functional groupselected from the group consisting of a hydroxyl group, an epoxy group,an amino group, a silanol group and an alkoxysilane group, saidfirst-order modified, hydrogenated polymer having the followingcharacteristics (i) to (iv): (i) a content of said vinyl aromatichydrocarbon monomer units of from 0 to 60% by weight, based on theweight of said hydrogenated polymer, (ii) a vinyl aromatic hydrocarbonblock ratio of from 0 to less than 50% by weight, wherein said vinylaromatic hydrocarbon block ratio is defined as the percent by weight ofthe vinyl aromatic hydrocarbon monomer units contained in said at leastone polymer block (H) of said vinyl aromatic hydrocarbon monomer units,based on the total weight of vinyl aromatic hydrocarbon monomer unitscontained in said copolymer (1-B), (iii) a weight average molecularweight of from 20,000 to 2,000,000, and (iv) a hydrogenation ratio ofmore than 70%, as measured with respect to the double bonds in saidconjugated diene monomer units.
 2. The first-order modified,hydrogenated polymer according to claim 1, wherein said functional groupcontaining first-order modifier group (2) comprises at least onefunctional group represented by a formula selected from the groupconsisting of the following formulae (a) to (m):

wherein, in the formulae (a) to (m): N represents a nitrogen atom, Sirepresents a silicon atom, 0 represents an oxygen atom, C represents acarbon atom, and H represents a hydrogen atom, each of R¹ to R⁴independently represents a hydrogen atom or a C₁-C₂₄ hydrocarbon groupwhich optionally has at least one functional group selected from thegroup consisting of a hydroxyl group, an epoxy group, an amino group, asilanol group and a C₁-C₂₄ alkoxysilane group, each R⁵ independentlyrepresents a C₁-C₄₈ hydrocarbon group and optionally, independently hasat least one functional group selected from the group consisting of ahydroxyl group, an epoxy group, an amino group, a silanol group and aC1-C24 alkoxysilane group, each R⁶ independently represents a hydrogenatom or a C₁-C8 alkyl group, wherein each of R¹ to R⁵ optionally,independently has bonded thereto at least one atom selected from thegroup consisting of an oxygen atom, a nitrogen atom, a sulfur atom and asilicon atom, said at least one atom being present in a linkage otherthan a hydroxyl group, an epoxy group, an amino group, a silanol groupand an alkoxysilane group.
 3. The first-order modified, hydrogenatedpolymer according to claim 1 or 2, which is represented by a polymerselected from the group consisting of the following formulae (I) to (V):

wherein: A¹ represents a unit which is represented by any one of thefollowing formulae (a-1) and (b-1):

B¹ represents a unit which is represented by the following formula(c-1):

C¹ represents a unit which is represented by any one of the followingformulae (d-1) and (e-1):

D¹ represents a unit which is represented by the following formula(f-1):(f-1) —R⁸—NHR³, E¹ represents a unit which is represented by thefollowing formula (g-1):(g-1) —R⁹—P¹, and F¹ represents a unit which is represented by any oneof the following formulae (h-1) to (j-1):

wherein, in the formulae (I) to (III) and (a-1) to (j-1): N represents anitrogen atom, Si represents a silicon atom, O represents an oxygenatom, C represents a carbon atom, and H represents a hydrogen atom, P¹represents said hydrogenated polymer (1), R^(1a) represents a trivalentaliphatic C₁-C₄₈ hydrocarbon group, each of R^(1b), R⁴, R⁸ to R¹⁰ andR¹³ to R¹⁵ independently represents a C₁-C₄₈ alkylene group, each of R²,R³ and R¹¹ independently represents a C₁-C₄₈ alkyl group, a C₆-C₄₈ arylgroup, an alkylaryl group comprised of C₁-C₄₈ alkyl and C₆-C₄₈ aryl, anaralkyl group comprised of C₁-C₄₈ alkyl and C₆-C₄₈ aryl, or a C₃-C₄₈cycloalkyl group, wherein each of R^(1a), R^(1b), R³, R⁴, R⁸ to R¹⁰ andR¹³ to R¹⁵ optionally, independently has at least one functional groupselected from the group consisting of a hydroxyl group, an epoxy group,an amino group, a silanol group and a C₁-C₂₄ alkoxysilane group, each ofR⁵ to R⁷ and R¹² independently represents a hydrogen atom, a C₁-C₄₈alkyl group, a C₆-C₄₈ aryl group, an alkylaryl group comprised of C₁-C₄₈alkyl and C₆-C₄₈ aryl, an aralkyl group comprised of C₁-C₄₈ alkyl andC₆-C₄₈ aryl, or a C₃-C₄₈ cycloalkyl group, wherein each of R^(1a),R^(1b), R² to R⁴ and R⁸to R¹⁵ optionally, independently has bondedthereto at least one atom selected from the group consisting of anoxygen atom, a nitrogen atom, a sulfur atom and a silicon atom, said atleast one atom being present in a linkage other than a hydroxyl group,an epoxy group, an amino group, a silanol group and an alkoxysilanegroup, and each of k, l, m and o is independently an integer of 0 ormore, provided that both k and l are not simultaneously 0, and n is aninteger of 1 or more.
 4. A filler-containing modified polymercomposition comprising: 100 parts by weight of (A-1) the first-ordermodified, hydrogenated polymer of claim 1, and 0.5 to 300 parts byweight of (B) a reinforcing filler.
 5. The filler-containing modifiedpolymer composition according to claim 4, which further comprises 0.01to 20 parts by weight of (C) a second-order modifier having a functionalgroup which is reactive to said functional group of said modifier groupof said first-order modified, hydrogenated polymer (A-1), wherein saidsecond-order modifier (C) is at least one member selected from the groupconsisting of a functional monomer and a functional oligomer.
 6. Thefiller-containing modified polymer composition according to claim 4 or5, wherein said reinforcing filler (B) is at least one member selectedfrom the group consisting of a silica inorganic filler, a metal oxide, ametal hydroxide and carbon.
 7. A crosslinked, filler-containing modifiedpolymer composition obtained by subjecting the filler-containingmodified polymer composition of claim 4 or 5 to a crosslinking reactionin the presence of a vulcanizing agent.
 8. A modified polymercomposition comprising: 1 to 99 parts by weight, relative to 100 partsby weight of the total of components (A-1) and (D), of (A-1) thefirst-order modified, hydrogenated polymer claim 1, and 99 to 1 part byweight, relative to 100 parts by weight of the total of components (A-1)and (D), of (D) at least one polymer selected from the group consistingof a thermoplastic resin other than said first-order modified,hydrogenated polymer (A-1) and a rubbery polymer other than saidfirst-order modified, hydrogenated polymer (A-1).
 9. The modifiedpolymer composition according to claim 8, which further comprises 0.01to 20 parts by weight, relative to 100 parts by weight of the total ofcomponents (A-1) and (D), of (C) a second-order modifier having afunctional group which is reactive to said functional group of saidmodifier group of said first-order modified, hydrogenated polymer (A-1),wherein said second-order modifier (C) is at least one member selectedfrom the group consisting of a functional monomer and a functionaloligomer.
 10. The modified polymer composition according to claim 8 or9, wherein said rubbery polymer in component (D) comprises at least onemember selected from the group consisting of a conjugated diene polymercomprising conjugated diene monomer units, a random copolymer comprisingconjugated diene monomer units and vinyl aromatic hydrocarbon monomerunits, a block copolymer comprising conjugated diene monomer units andvinyl aromatic hydrocarbon monomer units, a non-diene polymer and anatural rubber, said rubbery polymer being unhydrogenated or at leastpartially hydrogenated.
 11. The modified polymer composition accordingto claim 8 or 9, wherein said thermoplastic resin in component (D) is afunctional group-containing thermoplastic resin and said rubbery polymerin component (D) is a functional group-containing rubbery polymer,wherein each of said functional group-containing thermoplastic resin andrubbery polymer contains at least one functional group which is reactiveto said functional group of said first-order modifier group of saidfirst-order modified, hydrogenated polymer (A-1).
 12. The modifiedpolymer composition according to claim 1 1, wherein said functionalgroup-containing thermoplastic resin comprises at least one memberselected from the group consisting of a polyester resin, a polyamideresin, a polycarbonate resin, a polyurethane resin, a polyphenyleneether resin and a polyoxymethylene resin each of which contains at leastone functional group selected from the group consisting of an acidanhydride group, a carboxyl group, a hydroxyl group, an epoxy group, anamino group, a silanol group and an alkoxysilane group.
 13. An adhesivecomposition comprising: 100 parts by weight of (A-1) the first-ordermodified, hydrogenated polymer of claim 1, and 20 to 400 parts by weightof (E) a tackifier.
 14. The adhesive composition according to claim 13,which further comprises 0.01 to 20 parts by weight of (C) a second-ordermodifier having a functional group which is reactive to said functionalgroup of said modifier group of said first-order modified, hydrogenatedpolymer (A-1), wherein said second-order modifier (C) is at least onemember selected from the group consisting of a functional monomer and afunctional oligomer.
 15. An asphalt composition comprising: 0.5 to 50parts by weight of (A-1) the first-order modified, hydrogenated polymerclaim 1, and 100 parts by weight of (F) an asphalt.
 16. The asphaltcomposition according to claim 15, which further comprises 0.01 to 20parts by weight of (C) a second-order modifier having a functional groupwhich is reactive to said functional group of said modifier group ofsaid first-order modified, hydrogenated polymer (A-1), wherein saidsecond-order modifier (C) is at least one member selected from the groupconsisting of a functional monomer and a functional oligomer.
 17. Astyrene resin composition obtained by subjecting a raw material mixtureto radical polymerization, said raw material mixture comprising: 2 to 30parts by weight, relative to 100 parts by weight of the total ofcomponents (A-1) and (G), of (A-1) the first-order modified,hydrogenated polymer of claim 1, and 98 to 70 parts by weight, relativeto 100 parts by weight of the total of components (A-1) and (G), of (G)a vinyl aromatic hydrocarbon monomer or a mixture of a vinyl aromatichydrocarbon monomer and a comonomer copolymerizable with said vinylaromatic hydrocarbon monomer.
 18. The styrene resin compositionaccording to claim 17, wherein said raw material mixture furthercomprises 0.01 to 20 parts by weight, relative to 100 parts by weight ofthe total of components (A-1) and (G), of (C) a second-order modifierhaving a functional group which is reactive to said functional group ofsaid modifier group of said first-order modified, hydrogenated polymer(A-1), wherein said second-order modifier (C) is at least one memberselected from the group consisting of a functional monomer and afunctional oligomer.
 19. A method for producing the styrene resincomposition of claim 17 or 18, comprising: (1) providing a raw materialmixture comprising (A-1) the first-order modified, hydrogenated polymerof claim 1, (G) a vinyl aromatic hydrocarbon monomer or a mixture of avinyl aromatic hydrocarbon monomer and a comonomer copolymerizable withsaid vinyl aromatic hydrocarbon monomer, and optionally at least onemember selected from the group consisting of (C) a second-order modifierand (B) a reinforcing filler, and (2) subjecting said raw materialmixture to radical polymerization, thereby obtaining a styrene resincomposition.
 20. A second-order modified polymer comprising: (β) a basepolymer, and (δ) a functional group-containing modifier group bonded tosaid base polymer (β), wherein said second-order modified polymer isobtained by reacting a second-order modifier with a first-order modifiedpolymer comprising (β) a base polymer and (γ) a functionalgroup-containing first-order modifier group bonded to said base polymer(β) to thereby form (δ) a functional group-containing modifier group,wherein said second-order modifier has a functional group which isreactive to said functional group of said first-order modifier group (γ)of said first-order modified polymer, and wherein said second-ordermodifier is used in an amount of 0.3 to 10 moles, relative to oneequivalent of the functional group of said first-order modifier group(γ) of said first-order modified polymer, said second-order modifierbeing at least one member selected from the group consisting of afunctional monomer and a functional oligomer, wherein said base polymer(β) of said first-order modified polymer is unhydrogenated or at leastpartially hydrogenated and is at least one member selected from thegroup consisting of the following polymers (β-1) to (β-3): (β-1) aconjugated diene polymer comprising conjugated diene monomer units,(β-2) a copolymer comprising conjugated diene monomer units and vinylaromatic hydrocarbon monomer units, said copolymer having no or at leastone polymer block (H) of said vinyl aromatic hydrocarbon monomer units,wherein said copolymer has a vinyl aromatic hydrocarbon block ratio offrom 0 to less than 50% by weight, said vinyl aromatic hydrocarbon blockratio being defined as the percent by weight of the vinyl aromatichydrocarbon monomer units contained in said at least one polymer block(H) of said vinyl aromatic hydrocarbon monomer units, based on the totalweight of vinyl aromatic hydrocarbon monomer units contained in saidcopolymer as in the unhydrogenated state, and (β-3) a vinyl aromatichydrocarbon polymer comprising vinyl aromatic hydrocarbon monomer units,and wherein said functional group-containing first-order modifier group(γ) of said first-order modified polymer comprises at least onefunctional group represented by a formula selected from the groupconsisting of the following formulae (a) to (m):

wherein, in the formulae (a) to (m): N represents a nitrogen atom, Sirepresents a silicon atom, 0 represents an oxygen atom, C represents acarbon atom, and H represents a hydrogen atom, each of R¹ to R⁴independently represents a hydrogen atom or a C₁-C₂₄ hydrocarbon groupwhich optionally has at least one functional group selected from thegroup consisting of a hydroxyl group, an epoxy group, an amino group, asilanol group and a C₁-C₂₄ alkoxysilane group, each R⁵ independentlyrepresents a C₁-C₄₈ hydrocarbon group and optionally, independently hasat least one functional group selected from the group consisting of ahydroxyl group, an epoxy group, an amino group, a silanol group and aC₁,-C₂₄ alkoxysilane group, each R⁶ independently represents a hydrogenatom or a C₁-C₈ alkyl group, wherein each of R¹ to R⁵ optionally,independently has bonded thereto at least one atom selected from thegroup consisting of an oxygen atom, a nitrogen atom, a sulfur atom and asilicon atom, said at least one atom being present in a linkage otherthan a hydroxyl group, an epoxy group, an amino group, a silanol groupand an alkoxysilane group.
 21. The second-order modified polymeraccording to claim 20, wherein said first-order modified polymer isrepresented by a formula selected from the group consisting of thefollowing formulae (I) to (V):

wherein: A¹ represents a unit which is represented by any one of thefollowing formulae (a-1) and (b-1):

B¹ represents a unit which is represented by the following formula(c-1):

C¹ represents a unit which is represented by any one of the followingformulae (d-1) and (e-1):

D¹ represents a unit which is represented by the following formula(f-1):(f-1) —R⁸—NHR³, E¹ represents a unit which is represented by thefollowing formula (g-1):(g-1) —R⁹—P¹, and F¹ represents a unit which is represented by any oneof the following formulae (h-1) to -1):

wherein, in the formulae (I) to (III) and (a-1) to (j-1): N represents anitrogen atom, Si represents a silicon atom, 0 represents an oxygenatom, C represents a carbon atom, and H represents a hydrogen atom, P¹represents said base polymer, R^(1a) represents a trivalent aliphaticC₁-C₄₈ hydrocarbon group, each of R^(1b), R⁴, R⁸ to R¹⁰ and R¹³ to R¹⁵independently represents a C₁-C₄₈ alkylene group, each of R², R³ and R¹¹independently represents a C₁-C₄₈ alkyl group, a C₆-C₄₆ aryl group, analkylaryl group comprised of C₁-C₄₈ alkyl and C₆-C₄₈ aryl, an aralkylgroup comprised of C₃-C₄₈ alkyl and C₆-C₄₈ aryl, or a C₃-C₄8 cycloalkylgroup, wherein each of R^(1a), R^(1b), R³, R⁴, R⁸ to R¹⁰ and R¹³ to R¹⁵optionally, independently has at least one functional group selectedfrom the group consisting of a hydroxyl group, an epoxy group, an aminogroup, a silanol group and a C₁-C₂₄ alkoxysilane group, each of R⁵ to R⁷and R¹² independently represents a hydrogen atom, a C₁-C₄₈ alkyl group,a C₆-C₄₈ aryl group, an alkylaryl group comprised of C₁-C₄₈ alkyl andC₆-C₄₈ aryl, an aralkyl group comprised of C₁-C₄₈ alkyl and C₆-C₄₈ aryl,or a C₃-C₄8 cycloalkyl group, wherein each of R^(1a), R^(1b), R² to R⁴and R⁸ to R¹⁵ optionally, independently has bonded thereto at least oneatom selected from the group consisting of an oxygen atom, a nitrogenatom, a sulfur atom and a silicon atom, said at least one atom beingpresent in a linkage other than a hydroxyl group, an epoxy group, anamino group, a silanol group and an alkoxysilane group, and each of k,l, m and o is independently an integer of 0 or more, provided that bothk and l are not simultaneously 0, and n is an integer of 1 or more. 22.The second-order modified polymer according to claim 20 or 21, whereineach of said functional monomer and said functional oligomer has atleast one functional group selected from the group consisting of ahydroxyl group, an amino group, a carboxyl group, an acid anhydridegroup, an isocyanate group, an epoxy group, a silanol group and analkoxysilane group.
 23. The second-order modified polymer accordingclaim 20 or 21, which is represented by a formula selected from thegroup consisting of the following formulae (VI) to (X):

wherein A² represents a unit which is represented by any one of thefollowing formulae (a-2) and (b-2):

B² represents a unit which is represented by any one of the followingformulae (c-2) and (e-2):

C² represents a unit which is represented by any one of the followingformulae (f-2) to (f-2):

D² represents a unit which is represented by the following formula(i-2):(i-2) —R⁸—NR³-X¹, E² represents a unit which is represented by thefollowing formula (j-2):(j-2) —R⁹—P¹, and F² represents a unit which is represented by any oneof the following formulae (k-2) to (m-2):

wherein: X¹ represents a unit which is represented by any one of thefollowing formulae (n-2) to (s-2):

wherein, in the formulae (VI) to (VIII) and (a-2) to (s-2): N representsa nitrogen atom, Si represents a silicon atom, 0 represents an oxygenatom, C represents a carbon atom, and H represents a hydrogen atom, P¹represents the base polymer, R^(1a) represents a trivalent aliphaticC₁-C₄₈ hydrocarbon group, each of R^(1b), R^(4,) R⁸ to R¹⁰ and R¹³ toR²⁰ independently represents a C₁-C₄₈ alkylene group, each of R², R³ andR¹¹ independently represents a C₁-C₄₈ alkyl group, a C₆-C₄₈ aryl group,an alkylaryl group comprised of C₁-C₄₈ alkyl and C₆-C₄₈ aryl, an aralkylgroup comprised of C₁-C₄₈ alkyl and C₆-C₄₈ aryl, or a C₃-C₄₈ cycloalkylgroup, wherein each of R^(1a), R^(1b), R³, R⁴, R⁸ to R¹⁰, R¹³ to R¹⁵ andR¹⁷ to R²⁰ optionally, independently has at least one functional groupselected from the group consisting of a hydroxyl group, an epoxy group,an amino group, a silanol group and a C₁-C₂₄ alkoxysilane group, each ofR⁵ to R⁷ and R¹² independently represents a hydrogen atom, a C₁-C⁴⁸alkyl group, a C₆-C₄₈ aryl group, an alkylaryl group comprised of C₁-C₄8alkyl and C₆-C₄₈ aryl, an aralkyl group comprised of C₁-C₄₈ alkyl andC₆-C₄₈ aryl, or a C₃-C₄₈ cyclo-alkyl group, wherein each of R^(1a),R^(1b), R² to R⁴ and R⁸ to R²⁰ optionally, independently has bondedthereto at least one atom selected from the group consisting of anoxygen atom, a nitrogen atom, a sulfur atom, and a silicon atom, said atleast one atom being present in a linkage other than a hydroxyl group,an epoxy group, an amino group, a silanol group and an alkoxysilanegroup, and each of t, u, v and x is independently an integer of 0 ormore, provided that both t and u are not simultaneously 0, and each ofw, y, z and α is independently an integer of 1 or more.
 24. A method forproducing the second-order modified polymer claim 20, comprising: (1)providing a first-order modified polymer comprising: (β) a base polymerwhich is unhydrogenated or at least partially hydrogenated and which isat least one member selected from the group consisting of the followingpolymers (β-1) to (β-3): (β-1) a conjugated diene polymer comprisingconjugated diene monomer units, (β-2) a copolymer comprising conjugateddiene monomer units and vinyl aromatic hydrocarbon monomer units, saidcopolymer having no or at least one polymer block (H) of said vinylaromatic hydrocarbon monomer units, wherein said copolymer has a vinylaromatic hydrocarbon block ratio of from 0 to less than 50% by weight,said vinyl aromatic hydrocarbon block ratio being defined as the percentby weight of the vinyl aromatic hydrocarbon monomer units contained insaid at least one polymer block (H) of said vinyl aromatic hydrocarbonmonomer units, based on the total weight of vinyl aromatic hydrocarbonmonomer units contained in said copolymer as in the unhydrogenatedstate, and (β-3) a vinyl aromatic hydrocarbon polymer comprising vinylaromatic hydrocarbon monomer units, and (γ) a functionalgroup-containing first-order modifier group bonded to said base polymer(β), wherein said first-order modified polymer is produced by a processin which a base polymer having a living terminal is produced by a livinganionic polymerization using an organolithium compound as apolymerization catalyst, and a functional group-containing first-ordermodifier is addition-bonded to said living terminal of said base polymerto obtain a first-order modified polymer, optionally followed by partialor complete hydrogenation of the obtained first-order modified polymer,and (2) reacting a second-order modifier with said first-order modifiedpolymer to thereby form (δ) a functional group-containing modifiergroup, wherein said second-order modifier has a functional group whichis reactive to said functional group of said first-order modifier group(γ) of said first-order modified polymer, and wherein said second ordermodifier is used in an amount of 0.3 to 10 moles, relative to oneequivalent of said functional group of said first-order modifier group(γ) of said first-order modified polymer, thereby obtaining asecond-order modified polymer, wherein said functional group-containingfirst-order modifier group (γ) of said first-order modified polymercomprises at least one functional group represented by a formulaselected from the group consisting of the following formulae (a) to (m):

wherein, in the formulae (a) to (m): N represents a nitrogen atom, Sirepresents a silicon atom, 0 represents an oxygen atom, C represents acarbon atom, and H represents a hydrogen atom, each of R¹ to R⁴independently represents a hydrogen atom or a C₁-C₂₄ hydrocarbon groupwhich optionally has at least one functional group selected from thegroup consisting of a hydroxyl group, an epoxy group, an amino group, asilanol group and a C₁-C₂₄ alkoxysilane group, each R⁵ independentlyrepresents a C₁-C₄₈ hydrocarbon group and optionally, independently hasat least one functional group selected from the group consisting of ahydroxyl group, an epoxy group, an amino group, a silanol group and aC₁-C₂₄ alkoxysilane group, each R⁶ independently represents a hydrogenatom or a C₁-C₈ alkyl group, wherein each of R¹ to R⁵ optionally,independently has bonded thereto at least one atom selected from thegroup consisting of an oxygen atom, a nitrogen atom, a sulfur atom and asilicon atom, said at least one atom being present in a linkage otherthan a hydroxyl group, an epoxy group, an amino group, a silanol groupand an alkoxysilane group.
 25. A filler-containing modified polymercomposition comprising: 100 parts by weight of (A-2) the second-ordermodified polymer of claim 20, 0.5 to 300 parts by weight of (B) areinforcing filler.
 26. The filler-containing modified polymercomposition according to claim 25, wherein said reinforcing filler (B)is at least one member selected from the group consisting of a silicainorganic filler, a metal oxide, a metal hydroxide and carbon.
 27. Acrosslinked, filler-containing modified polymer composition obtained bysubjecting the filler-containing modified polymer composition of claim25 or 26 to a crosslinking reaction in the presence of a vulcanizingagent.
 28. A modified polymer composition comprising: 1 to 99 parts byweight, relative to 100 parts by weight of the total of components (A-2)and (D), of (A-2) the second-order modified polymer of claim 20, and 99to 1 part by weight, relative to 100 parts by weight of the total ofcomponents (A-2) and (D), of (D) at least one polymer selected from thegroup consisting of a thermoplastic resin other than said second-ordermodified polymer (A-2) and a rubbery polymer other than saidsecond-order modified polymer (A-2).
 29. The modified polymercomposition according to claim 28, wherein said thermoplastic resin incomponent (D) comprises at least one member selected from the groupconsisting of a polyester resin, a polyamide resin, a polycarbonateresin, a polyurethane resin, a polyphenylene ether resin and apolyoxymethylene resin each of which contains at least one functionalgroup selected from the group consisting of an acid anhydride group, acarboxyl group, a hydroxyl group, an epoxy group, an amino group, asilanol group and an alkoxysilane group.
 30. A crosslinked, modifiedpolymer composition obtained by subjecting the modified polymercomposition of any one of claim 28 or 29 to melt-kneading in thepresence of a vulcanizing agent.
 31. An adhesive composition comprising:100 parts by weight of (A-2) the second-order modified polymer of anyone of claim 20, and 20 to 400 parts by weight of (E) a tackifier. 32.An asphalt composition comprising: 0.5 to 50 parts by weight of (A-2)the second-order modified polymer of claim 20, and 100 parts by weightof (F) an asphalt.
 33. A styrene resin composition obtained bysubjecting a raw material mixture to radical polymerization, said rawmaterial mixture comprising: 2 to 30 parts by weight, relative to 100parts by weight of the total of components (A-2) and (G), of (A-2) thesecond-order modified polymer of any one of claim 20, and 98 to 70 partsby weight, relative to 100 parts by weight of the total of components(A-2) and (G), of (G) a vinyl aromatic hydrocarbon monomer or a mixtureof a vinyl aromatic hydrocarbon monomer and a comonomer copolymerizablewith said vinyl aromatic hydrocarbon monomer.
 34. The styrene resincomposition according to claim 33, wherein said raw material mixturefurther comprises 0.5 to 300 parts by weight, relative to 100 parts byweight of component (A-2), of (B) a reinforcing filler.
 35. The styreneresin composition according to claim 34, wherein said reinforcing filler(B) is at least one member selected from the group consisting of asilica inorganic filler, a metal oxide, a metal hydroxide and carbon.36. A filler-containing modified polymer composition comprising: 100parts by weight of (A-3) a first-order modified polymer comprising: (β)a base polymer which is unhydrogenated or at least partiallyhydrogenated and which is at least one member selected from the groupconsisting of the following polymers (β-1) to (β-3): (β-1) a conjugateddiene polymer comprising conjugated diene monomer units, (β-2) acopolymer comprising conjugated diene monomer units and vinyl aromatichydrocarbon monomer units, said copolymer having no or at least onepolymer block (H) of said vinyl aromatic hydrocarbon monomer units,wherein said copolymer has a vinyl aromatic hydrocarbon block ratio offrom 0 to less than 50% by weight, said vinyl aromatic hydrocarbon blockratio being defined as the percent by weight of the vinyl aromatichydrocarbon monomer units contained in said at least one polymer block(H) of said vinyl aromatic hydrocarbon monomer units, based on the totalweight of vinyl aromatic hydrocarbon monomer units contained in saidcopolymer as in the unhydrogenated state, and (β-3) a vinyl aromatichydrocarbon polymer comprising vinyl aromatic hydrocarbon monomer units,and (γ) a functional group-containing first-order modifier group bondedto said base polymer (β), 0.5 to 300 parts by weight of (B) areinforcing filler, and 0.01 to 20 parts by weight of (C) a second-ordermodifier having a functional group which is reactive to said functionalgroup of said first-order modifier group (γ) of said first-ordermodified polymer (A-3), wherein said second-order modifier (C) is atleast one member selected from the group consisting of a functionalmonomer and a functional oligomer, wherein said functionalgroup-containing first-order modifier group (γ) of said first-ordermodified polymer (A-3) comprises at least one functional grouprepresented by a formula selected from the group consisting of thefollowing formulae (a) to (m):

wherein, in the formulae (a) to (m): N represents a nitrogen atom, Sirepresents a silicon atom, 0 represents an oxygen atom, C represents acarbon atom, and H represents a hydrogen atom, each of R¹ to R⁴independently represents a hydrogen atom or a C₁-C₂₄ hydrocarbon groupwhich optionally has at least one functional group selected from thegroup consisting of a hydroxyl group, an epoxy group, an amino group, asilanol group and a C₁-C₂₄ alkoxysilane group, each R⁵ independentlyrepresents a C₁-C₄₈ hydrocarbon group and optionally, independently hasat least one functional group selected from the group consisting of ahydroxyl group, an epoxy group, an amino group, a silanol group and aC₁-C₂₄ alkoxysilane group, each R⁶ independently represents a hydrogenatom or a C₁-C₈ alkyl group, wherein each of R¹ to R⁵ optionally,independently has bonded thereto at least one atom selected from thegroup consisting of an oxygen atom, a nitrogen atom, a sulfur atom and asilicon atom, said at least one atom being present in a linkage otherthan a hydroxyl group, an epoxy group, an amino group, a silanol groupand an alkoxysilane group.
 37. The filler-containing modified polymercomposition according to claim 36, wherein said reinforcing filler (B)is at least one member selected from the group consisting of a silicainorganic filler, a metal oxide, a metal hydroxide and carbon.
 38. Acrosslinked, filler-containing modified polymer composition obtained bysubjecting the filler-containing modified polymer composition of claim36 or 37 to a crosslinking reaction in the presence of a vulcanizingagent.
 39. A modified polymer composition comprising: 1 to 99 parts byweight, relative to 100 parts by weight of the total of components (A-3)and (D), of (A-3) a first-order modified polymer comprising: (β) a basepolymer which is unhydrogenated or at least partially hydrogenated andwhich is at least one member selected from the group consisting of thefollowing polymers (β-1) to (β-3): (β-1) a conjugated diene polymercomprising conjugated diene monomer units, (β-2) a copolymer comprisingconjugated diene monomer units and vinyl aromatic hydrocarbon monomerunits, said copolymer having no or at least one polymer block (H) ofsaid vinyl aromatic hydrocarbon monomer units, wherein said copolymerhas a vinyl aromatic hydrocarbon block ratio of from 0 to less than 50%by weight, said vinyl aromatic hydrocarbon block ratio being defined asthe percent by weight of the vinyl aromatic hydrocarbon monomer unitscontained in said at least one polymer block (H) of said vinyl aromatichydrocarbon monomer units, based on the total weight of vinyl aromatichydrocarbon monomer units contained in said copolymer as in theunhydrogenated state, and (β-3) a vinyl aromatic hydrocarbon polymercomprising vinyl aromatic hydrocarbon monomer units, and (γ) afunctional group-containing first-order modifier group bonded to saidbase polymer (β), 99 to 1 part by weight, relative to 100 parts byweight of the total of components (A-3) and (D), of (D) at least onepolymer selected from the group consisting of a thermoplastic resinother than said first-order modified polymer (A-3) and a rubbery polymerother than said first-order modified polymer (A-3), and 0.01 to 20 partsby weight, relative to 100 parts by weight of the total of components(A-3) and (D), of (C) a second-order modifier having a functional groupwhich is reactive to said functional group of said first-order modifiergroup (γ) of said first-order modified polymer (A-3), wherein saidsecond-order modifier (C) is at least one member selected from the groupconsisting of a functional monomer and a functional oligomer, whereinsaid functional group-containing first-order modifier group (γ) of saidfirst-order modified polymer (A-3) comprises at least one functionalgroup represented by a formula selected from the group consisting of thefollowing formulae (a) to (m):

wherein, in the formulae (a) to (m): N represents a nitrogen atom, Sirepresents a silicon atom, 0 represents an oxygen atom, C represents acarbon atom, and H represents a hydrogen atom, each of R¹ to R⁴independently represents a hydrogen atom or a C₁-C₂₄ hydrocarbon groupwhich optionally has at least one functional group selected from thegroup consisting of a hydroxyl group, an epoxy group, an amino group, asilanol group and a C₁-C₂₄ alkoxysilane group, each R⁵ independentlyrepresents a C₁-C₄₈ hydrocarbon group and optionally, independently hasat least one functional group selected from the group consisting of ahydroxyl group, an epoxy group, an amino group, a silanol group and aC₁-C₂₄ alkoxysilane group, each R⁶ independently represents a hydrogenatom or a C₁-C₈ alkyl group, wherein each of R¹ to R⁵ optionally,independently has bonded thereto at least one atom selected from thegroup consisting of an oxygen atom, a nitrogen atom, a sulfur atom and asilicon atom, said at least one atom being present in a linkage otherthan a hydroxyl group, an epoxy group, an amino group, a silanol groupand an alkoxysilane group.
 40. The modified polymer compositionaccording to claim 39, wherein said thermoplastic resin in component (D)comprises at least one member selected from the group consisting of apolyester resin, a polyamide resin, a polycarbonate resin, apolyurethane resin, a polyphenylene ether resin and a polyoxymethyleneresin each of which contains at least one functional group selected fromthe group consisting of an acid anhydride group, a carboxyl group, ahydroxyl group, an epoxy group, an amino group, a silanol group and analkoxysilane group.
 41. A crosslinked, modified polymer compositionobtained by subjecting the modified polymer composition of claim 39 or40 to melt-kneading in the presence of a vulcanizing agent.
 42. Anadhesive composition comprising: 100 parts by weight of (A-3) afirst-order modified polymer comprising: (β) a base polymer which isunhydrogenated or at least partially hydrogenated and which is at leastone member selected from the group consisting of the following polymers(β-1) to (β-3): (β-1) a conjugated diene polymer comprising conjugateddiene monomer units, (β-2) a copolymer comprising conjugated dienemonomer units and vinyl aromatic hydrocarbon monomer units, saidcopolymer having no or at least one polymer block (H) of said vinylaromatic hydrocarbon monomer units, wherein said copolymer has a vinylaromatic hydrocarbon block ratio of from 0 to less than 50% by weight,said vinyl aromatic hydrocarbon block ratio being defined as the percentby weight of the vinyl aromatic hydrocarbon monomer units contained insaid at least one polymer block (H) of said vinyl aromatic hydrocarbonmonomer units, based on the total weight of vinyl aromatic hydrocarbonmonomer units contained in said copolymer as in the unhydrogenatedstate, and (β-3) a vinyl aromatic hydrocarbon polymer comprising vinylaromatic hydrocarbon monomer units, and (γ) a functionalgroup-containing first-order modifier group bonded to said base polymer(β), 20 to 400 parts by weight of (E) a tackifier, and 0.01 to 20 partsby weight of (C) a second-order modifier having a functional group whichis reactive to said functional group of said first-order modifier group(γ) of said first-order modified polymer (A-3), wherein saidsecond-order modifier (C) is at least one member selected from the groupconsisting of a functional monomer and a functional oligomer, whereinsaid functional group-containing first-order modifier group (γ) of saidfirst-order modified polymer (A-3) comprises at least one functionalgroup represented by a formula selected from the group consisting of thefollowing formulae (a) to (m):

wherein, in the formulae (a) to (m): N represents a nitrogen atom, Sirepresents a silicon atom, 0 represents an oxygen atom, C represents acarbon atom, and H represents a hydrogen atom, each of R¹ to R⁴independently represents a hydrogen atom or a C₁-C₂₄ hydrocarbon groupwhich optionally has at least one functional group selected from thegroup consisting of a hydroxyl group, an epoxy group, an amino group, asilanol group and a C₁-C₂₄ alkoxysilane group, each R⁵ independentlyrepresents a C₁-C₄₈ hydrocarbon group and optionally, independently hasat least one functional group selected from the group consisting of ahydroxyl group, an epoxy group, an amino group, a silanol group and aC₁-C₂₄ alkoxysilane group, each R⁶ independently represents a hydrogenatom or a C₁-C₈ alkyl group, wherein each of R¹ to R⁵ optionally,independently has bonded thereto at least one atom selected from thegroup consisting of an oxygen atom, a nitrogen atom, a sulfur atom and asilicon atom, said at least one atom being present in a linkage otherthan a hydroxyl group, an epoxy group, an amino group, a silanol groupand an alkoxysilane group.
 43. An asphalt composition comprising: 0.5 to50 parts by weight of (A-3) a first-order modified polymer comprising:(β) a base polymer which is unhydrogenated or at least partiallyhydrogenated and which is at least one member selected from the groupconsisting of the following polymers (β-1) to (β-3): (β-1) a conjugateddiene polymer comprising conjugated diene monomer units, (β-2) acopolymer comprising conjugated diene monomer units and vinyl aromatichydrocarbon monomer units, said copolymer having no or at least onepolymer block (H) of said vinyl aromatic hydrocarbon monomer units,wherein said copolymer has a vinyl aromatic hydrocarbon block ratio offrom 0 to less than 50% by weight, said vinyl aromatic hydrocarbon blockratio being defined as the percent by weight of the vinyl aromatichydrocarbon monomer units contained in said at least one polymer block(H) of said vinyl aromatic hydrocarbon monomer units, based on the totalweight of vinyl aromatic hydrocarbon monomer units contained in saidcopolymer as in the unhydrogenated state, and (β-3) a vinyl aromatichydrocarbon polymer comprising vinyl aromatic hydrocarbon monomer units,and (γ) a functional group-containing first-order modifier group bondedto said base polymer (β), 100 parts by weight of (F) an asphalt, and0.01 to 20 parts by weight of (C) a second-order modifier having afunctional group which is reactive to said functional group of saidfirst-order modifier group (γ) of said first-order modified polymer(A-3), wherein said second-order modifier (C) is at least one memberselected from the group consisting of a functional monomer and afunctional oligomer, wherein said functional group-containingfirst-order modifier group (γ) of said first-order modified polymer(A-3) comprises at least one functional group represented by a formulaselected from the group consisting of the following formulae (a) to (m):

wherein, in the formulae (a) to (m): N represents a nitrogen atom, Sirepresents a silicon atom, O represents an oxygen atom, C represents acarbon atom, and H represents a hydrogen atom, each of R¹ to R⁴independently represents a hydrogen atom or a C₁-C₂₄ hydrocarbon groupwhich optionally has at least one functional group selected from thegroup consisting of a hydroxyl group, an epoxy group, an amino group, asilanol group and a C₁-C₂₄ alkoxysilane group, each R⁵ independentlyrepresents a C₁-C₄₈ hydrocarbon group and optionally, independently hasat least one functional group selected from the group consisting of ahydroxyl group, an epoxy group, an amino group, a silanol group and aC₁-C₂₄ alkoxysilane group, each R⁶ independently represents a hydrogenatom or a C₁-C₈ alkyl group, wherein each of R¹ to R⁵ optionally,independently has bonded thereto at least one atom selected from thegroup consisting of an oxygen atom, a nitrogen atom, a sulfur atom and asilicon atom, said at least one atom being present in a linkage otherthan a hydroxyl group, an epoxy group, an amino group, a silanol groupand an alkoxysilane group.
 44. A styrene resin composition obtained bysubjecting a raw material mixture to radical polymerization, said rawmaterial mixture comprising: 2 to 30 parts by weight, relative to 100parts by weight of the total of components (A-3) and (G), of (A-3) afirst-order modified polymer comprising: (β) a base polymer which isunhydrogenated or at least partially hydrogenated and which is at leastone member selected from the group consisting of the following polymers(β-1) to (β-3): (β-1) a conjugated diene polymer comprising conjugateddiene monomer units, (β-2) a copolymer comprising conjugated dienemonomer units and vinyl aromatic hydrocarbon monomer units, saidcopolymer having no or at least one polymer block (H) of said vinylaromatic hydrocarbon monomer units, wherein said copolymer has a vinylaromatic hydrocarbon block ratio of from 0 to less than 50% by weight,said vinyl aromatic hydrocarbon block ratio being defined as the percentby weight of the vinyl aromatic hydrocarbon monomer units contained insaid at least one polymer block (H) of said vinyl aromatic hydrocarbonmonomer units, based on the total weight of vinyl aromatic hydrocarbonmonomer units contained in said copolymer as in the unhydrogenatedstate, and (β-3) a vinyl aromatic hydrocarbon polymer comprising vinylaromatic hydrocarbon monomer units, and (γ) a functionalgroup-containing first-order modifier group bonded to said base polymer(β), 98 to 70 parts by weight, relative to 100 parts by weight of thetotal of components (A-3) and (G), of (G) a vinyl aromatic hydrocarbonmonomer or a mixture of a vinyl aromatic hydrocarbon monomer and acomonomer copolymerizable with said vinyl aromatic hydrocarbon monomer,and 0.01 to 20 parts by weight, relative to 100 parts by weight of thetotal of components (A-3) and (G), of (C) a second-order modifier havinga functional group which is reactive to said functional group of saidfirst-order modifier group (γ) of said first-order modified polymer(A-3), wherein said second-order modifier (C) is at least one memberselected from the group consisting of a functional monomer and afunctional oligomer wherein said functional group-containing first-ordermodifier group (γ) of said first-order modified polymer (A-3) comprisesat least one functional group represented by a formula selected from thegroup consisting of the following formulae (a) to (m):

wherein, in the formulae (a) to (m): N represents a nitrogen atom, Sirepresents a silicon atom, O represents an oxygen atom, C represents acarbon atom, and H represents a hydrogen atom, each of R¹ to R⁴independently represents a hydrogen atom or a C₁-C₂₄ hydrocarbon groupwhich optionally has at least one functional group selected from thegroup consisting of a hydroxyl group, an epoxy group, an amino group, asilanol group and a C₁-C₂₄ alkoxysilane group, each R⁵ independentlyrepresents a C₁-C₄₈ hydrocarbon group and optionally, independently hasat least one functional group selected from the group consisting of ahydroxyl group, an epoxy group, an amino group, a silanol group and aC₁-C₂₄ alkoxysilane group, each R⁶ independently represents a hydrogenatom or a C₁-C₈ alkyl group, wherein each of R¹ to R⁵ optionally,independently has bonded thereto at least one atom selected from thegroup consisting of an oxygen atom, a nitrogen atom, a sulfur atom and asilicon atom, said at least one atom being present in a linkage otherthan a hydroxyl group, an epoxy group, an amino group, a silanol groupand an alkoxysilane group.
 45. The styrene resin composition accordingto claim 44, wherein said raw material mixture further comprises 0.5 to300 parts by weight, relative to 100 parts by weight of component (A-3),of (B) a reinforcing filler.
 46. The styrene resin composition accordingto claim 45, wherein said reinforcing filler (B) is at least one memberselected from the group consisting of a silica inorganic filler, a metaloxide, a metal hydroxide and carbon.